Lactone-modified, Mannich base dispersant additives useful in oleaginous compositions

ABSTRACT

Poly (C 5  -C 9  lactone) modified Mannich base adducts are made by reacting a C 5  -C 9  lactone, an amine, an aldehyde, an N-hydroxyarylamine, and a hydrocarbyl substituted C 4  -C 10  monounsaturated dicarboxylic acid producing material, e.g., a polyisobutenyl succinic anhydride, which, in turn, preferably is made by reacting a polymer of a C 2  to C 10  monoolefin, preferably polyisobutylene, having a molecular weight of about 700 to 10,000 with a C 4  to C 10  monounsaturated acid, anhydride or ester, preferably maleic anhydride, such that there are about 0.7 to 2.00 dicarboxylic acid producing moieties per molecule of said olefin polymer used in the reaction mixture. The resulting adducts are useful per se as oil soluble dispersant additives. They are also useful in fuel and lubricating oil compositions, as well as in concentrates and additive packages.

RELATED U.S. APPLICATIONS

This application is related to the following applications filed by theinventors herein: Ser. No. 916,218, Ser. No. 916,114, Ser. No. 916,113,Ser. No. 916,287, Ser. No. 916,108, Ser. No. 916,303 and Ser. No.916,217, all of which applications were filed on Oct. 7, 1986. Thisapplication is also related to Ser. No. 077716, filed on July 24, 1987by the inventors herein. All of these related applications are expresslyincorporated herein by reference in their entirety.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates to oil soluble dispersant additives useful infuel and lubricating oil compositions, including concentrates containingsaid additives, and methods for their manufacture and use. Thedispersant additives are poly (C₅ -C₉ lactone) modified Mannich baseadducts which are prepared from moieties of N-hydroxyaryl amine, di- orpolyamine, high molecular weight hydrocarbyl-substituted dicarboxylicacid material, aldehyde and C₅ C₉ lactone. The high molecular weighthydrocarbon group has a number average molecular weight (M_(n)) of about700 to about 10,000. The additives will have a ratio (functionality) ofabout 0.70 to about 2.0 dicarboxylic acid producing moieties for eachequivalent weight of the high molecular weight hydrocarbon therein.

2. Prior Art

It is known that polymers of 6 to 10 membered lactones such asvalerolactone or epsilon-caprolactone, hereinafter E-caprolactone, canbe prepared by reacting the lactone monomer with a hydroxyl or amineinitiator. When reacting E-carprolactone, for example, thepolymerization reaction may be illustrated by the following equations:##STR1##

The reactions are known to be catalyzed by various esterificationcatalysts such as stannous octanoate, and a variety of differentmolecular weight products are feasible depending upon the ratio oflactone to initiator. Molecular weights on the order of from a fewhundred up to about 5,000 are reproducably achievable.

Caprolactone can also be polymerized to a very high molecular weight,e.g., on the order of 100,000 or more. Typically such high molecularweight polymers do not employ initiators and preservation offunctionality is not a requirement.

It is also known to react a lactone such as E-caprolactone with adiamine wherein one of the diamine groups is a tertiary amine and theother amine group is a primary or secondary amine to form apolycaprolactone polymer having a tertiary amine group at one end and aprimary hydroxyl group at the other end. The polycaprolactone polymerwould be used to neutralize polymeric acids.

U.S. Pat. No. 4,354,950 discloses a method of preparing Mannich basederivatives of hydroxyaryl succinimides of the formula ##STR2## where Ris hydrocarbyl of 25 to 200 carbons, R' is H, alkyl or halogen, "n" is 2or 3, "m" has a value of 1 to 5, Y is H or a methylene hydroxyarylsuccinimide radical, "x" has a value of 1 to 2 when Y is H and a valueof 1 when Y is a methylene hydroxyarl succinimide radical. The abovesuccinimides are formed in a stepwise reaction, e.g., by reacting apolyalkenyl succinic anhydride with an aminophenol, to produce anintermediate N-(hydroxyaryl) hydrocarbyl succinimide, which is thenreacted with an alkylene diamine or polyalkylene polyamine and analdehyde (e.g., formaldehyde) in a Mannich base reaction to produce thedescribed succinimides. The described succinimides may be added to abase oil of lubricating viscosity to form lubricant concentrates andlubricating oil formulations.

It has now been found that oil soluble dispersant additives, useful infuel and lubricating oil compositions, including concentrates containingthe additives, can be prepared by polymerizing a 6 to 10 memberedlactone using as the initiator those lactone-reactive functionscontained within the class of oil soluble Mannich base derivativesdisclosed, for example, in U.S. Pat. No. 4,354.950.

While there are a number of prior art disclosures relating to Mannichbase dispersants and to lactone polymerization reactions, in general,little or no prior art of direct pertinence appears to have surfaced inregard to the present dispersants. Exemplary of the patent literaturewhich relates to lactone polymerization processes and/or to oil solubledispersant additives are the following U.S. Patents: U.S. Pat. No.4,362,635 discloses synthetic ester oils which are esterificationproducts of monoalcohols and dicarboxylic acids or of polyhydricalcohols and monocarboxylic acids respectively, containing 5 to 45% byweight of units of hydroxycarboxylic acids obtained from aliphaticalcohols, aliphatic, cycloaliphatic or aromatic carboxylic acids, andlactones of aliphatic C₅ -C₁₂ hydroxycarboxylic acids. The syntheticester oils are suitable for the preparation of lubricants and lubricantcompositions.

U.S. Pat. No. 3,202,678 discloses as oil additives, N-polyaminesubstituted alkenyl succinimides, wherein the alkenyl radical isobtained by polymerizing a C₂ -C₅ olefin to form a hydrocarbon having amolecular weight ranging from about 400 to about 3000. The number ofdicarboxylic acid producing moieties per hydrocarbon radical in thesuccinimides is not disclosed, but the mole ratio of polyolefin tomaleic anhydride used to obtain the alkenyl succinimides is from 1:1 to1:10.

U.S. Pat. No. 3,219,666 discloses as dispersing agents in lubricants,derivatives of polyalkenyl succinic acids and nitrogen compounds,including polyamines. The preferred molecular weight of the polyalkenylmoieties is 750-5,000.

U.S. Pat. No. 4,234,435 discloses as oil additives, polyalkylenesubstituted dicarboxylic acids derived from polyalkylenes having a M_(n)of 1300 to 5,000 and containing at least 1.3 dicarboxylic acid groupsper polyalkylene. In Example 34 of that patent, apolyisobutene-substituted succinic acylating agent is reacted withcaprolactam in the presence of mineral oil and sodium hydroxide.

U.S. Pat. No. 3,381,022 relates to ester derivatives of substantiallysaturated polymerized olefin-substituted succinic acid wherein thepolymerized olefin substituent contains at least about 50 aliphaticcarbon atoms and as a molecular weight of about 700 to 5000. The estersinclude the acidic esters, diesters, and metal salt esters wherein theester moiety is derived from monohydric and polyhydric alcohols, phenolsand naphthols. The ester derivatives are useful as additives inlubricating compositions, fuels, hydrocarbon oils and power transmissionfluids. A related application, i.e., U.S. Pat. No. 3,522,179, relates tolubricating compositions comprising a major amount of a lubricating oiland a minor proportion of an ester derivative of ahydrocarbon-substituted succinic acid sufficient to improve thedetergency of the lubricating composition. The ester derivatives aresimilar to those described in U.S. Pat. No. 3,381,022 and contain atleast about 50 aliphatic carbon atoms. The hydrocarbon substituent maybe derived from a polymerized lower monoolefin having a molecular weightof from about 700 to about 5,000.

U.S. Pat. No. 4,502,970 discloses lubricating oil compositions useful inboth gasoline engines and diesel engines. The compositions contain apolyisobutenyl succinicimide as a supplemental dispersant-detergent incombination with another conventional dispersant. The polyisobutenylgroup has a M_(n) of about 700-5,000.

U.S. Pat. No. 4,379,914 and its continuation-in-part (U.S. Pat. No.4,463,168) disclose the preparation of polycaprolactone polymers byreacting E-caprolactone with a diamine wherein one of the amine groupsof the diamine is a tertiary amine and the other is a primary orsecondary amine. The polycaprolactone polymers are disclosed as beinguseful for neutralizing certain sulfonic acid-containing polymers toform amine-neutralized sulfonated derivatives.

U.S. Pat. No. 3,169,945 discloses the preparation of lactone polyesterswhich are useful as plasticizers and as intermediates for preparingelastomers and foams. The polyesters can be prepared by reacting alactone such as E-caprolactone with an initiator such as an alcohol,amine or amino alcohol.

U.S. Pat. No. 4,532,058 discloses as a motor oil dispersant, aspirolactone condensation product formed by heating alkenyl succinicanhydrides in the presence of a basic catalyst, and then heating theresulting bicyclic spirodilactone condensation product with a polyamineor polyamine alcohol. It should be emphasized that this patent describesthe intermolecular decaboxylation of an alkenyl succinic anhydride atelevated temperatures to form a condensation product and carbon dioxideas a by-product. This prior art is not concerned with polymerizablelactones which are the subject of the instant invention.

U.S. Pat. Nos. 4,113,639 and 4,116,876 disclose an example of alkenylsuccinic anhydride having a molecular weight of the alkenyl group of1,300 and a Saponification Number of 103 (about 1.3 succinic anhydrideunits per hydrocarbon molecule). This alkenyl succinic anhydride may bereacted with polyamine and then boric acid (U.S. Pat. No. 4,113,639), ormay be reacted with an amino alcohol to form an oxazoline (U.S. Pat. No.4,116,876) which is then borated by reaction with boric acid.

U.S. Pat. No. 4,062,786 in Example 13 shows a polyisobutenylsuccinicanhydride of molecular weight of about 1300 and a Saponification Numberof about 100 (about 1.25 succinic anhydride units per alkenyl group).

U.S. Pat. No. 4,123,373 in Example 3 shows a polyisobutenylsuccinicanhydride of about 1,400 molecular weight having a Saponification Numberof 80 (about 1.07 succinic anhydride units per polyisobutylene units).

U.S. Pat. No. 3,442,808 relates to lubricating oil additives prepared byreacting alkenyl succinic anhydride with the Mannich condensationproduct prepared by condensing alkyl substituted phenol, formaldehydeand polyalkylene polymaine.

U.S. Pat. No. 3,649,229 relates to reaction products obtained from highmolecular weight alkyl-substituted hydroxy aromatic compounds, aminesand aldehydes, which are disclosed to be useful as detergency improversfor liquid hydrocarbon fuels.

U.S. Pat. No. 3,798,165 relates to oil soluble high molecular weightMannich condensation products formed by reacting certain high molecularweight alkyl-substituted hydroxy aromatic compounds, with a compoundcontaining at least a HN<group (e.g., an alkylene polyamine) and analdehyde (e..g, formaldehyde).

U.S. Pat. No. 4,338,471 discloses a process for preparing substitutedcarboxylic acids and their derivatives succinic anhydride in which thesynthesis reaction is carried out at least partially thermally in thepresence of a furan-type compound. A similar process is disclosed inU.S. Pat. No. 4,450,281 wherein an alkenylsuccinic anhydride is madefrom a hydrocarbon with at least two double bonds, such as anethylene-propylene-butadiene terpolymer. The products of these patentsare useful as viscosity index improvers.

U.S. Pat. No. 4,584,117 and its division (U.S. Pat. No. 4,624,681)disclose additives which are useful as dispersants in lubricating oils,gasolines, marine crankcase oils and hydraulic fluids. The additives areprepared by first reacting a polyamine with a cyclic carbonate to forman intermediate, followed by reaction of this intermediate with analkenyl or alkyl succinic anhydride.

U.S. Pat. No. 4,585,566 relates to nitrogen-containing dispersantadditives having at least one primary or secondary amine group whichhave been modified by treatment with a cyclic carbonate. Examples of thenitrogen-containing dispersants which are so modified includepolyoxyalkylene polyamines, Mannich bases, borated Mannich bases andhydrocarbyl sulfonamides having at least one additional amino group.

U.S. Pat. No. 4,612,132 related additives which are useful asdispersants and lubricating oils, gasolines and the like. The additivespolyamino alkenyl or alkyl succinimides which have been reacted withcyclic carbonates, linear mono- or polycarbonates, or chloroformate tointroduce carbonate functionality.

U.S. Pat. No. 4,614,603 is directed to polyamino alkenyl or alkylsuccinimides which have been modified by treatment with a thiolactam,lactam or thiolactone. The modified materials are useful as dispersantsor detergents in lubricating oils.

U.S. Pat. No. 4,617,138 relates to polyamino alkenyl or alkylsuccinimides which have been modified by treatment with a lactone toyield modified succinimides with a hydrocarbylcarbonylalkylene group.The modified succinimides are useful as dispersants in lubricating oils,gasolines, marine crankcase oils and hydraulic oils. The lactones whichare disclosed as being suitable for treating the succinimides arelimited to 2-hydrocarbylcarbonyl substituted lactones which may beprepared, for example, by reacting an ester and a lactone, such as gammabutyrolactone or valerolactone in the presence of an organic orinorganic base.

European Pat. No. 202,024 relates to additives which are useful asdispersants in lubricating oils and hydrocarbon fuels and which areobtained by treating polyamino alkenyl or alkyl succinimides with acyclic carbonate, thiocarbomate, or dithiocarbomate.

U.S. Pat. No. 4,645,525 discloses polyamine alkenyl or alkylsuccinimides which have been modified by treatment with a lactone toyield polyamino alkenyl or alkyl succinimides wherein one or more of thebasic nitrogens of the polyamino moiety is substituted with ahydroxyalkylene carbonyl group. The additives so disclosed are useful asdispersants in lubricating oils, gasolines, marine crank case oils andhydraulic oils.

U.S. Pat. No. 4,647,390 relates to additives which are useful asdispersants and detergents in lubricating oils and fuels. The additivesare polyamino alkenyl or alkyl succinimides wherein one or more of theamino nitrogens of the succinimide is substituted with ##STR3## whereinR₄ is hydrocarbyl of from 1 to 30 carbon atoms; R₅ is hydrocarbyl offrom 2 to 30 carbon atoms or --R₆ --(OR₆)_(p) --, where R₆ is alkyleneof 2 to 5 carbon atoms and p is an integer from 1 to 100; and m is aninteger of from 0 to 1.

U.S. Pat. No. 4,663,062 discloses polyaminoalkenyl or alkyl succinimideswhich have been modified by treatment with a compound of the formula:##STR4## wherein W is oxygen or sulfur; X is oxygen or sulfur; R₄ is analkylene group of from 2 to 3 carbon atoms or an alkylene group of from2 to 3 carbon atoms substituted with from 1 to 3 alkyl groups of from 1to 2 carbon atoms each; and R₅ is hydrogen or alkyl of from 1 to 20carbon atoms. The modified polyamino alkenyl or alkyl succinimidespossess dispersancy and detergency in lubricating oils and in fuels.Similar disclosures are contained in U.S. Pat. Nos. 4,666,459 and4,666,460.

U.S. Pat. No. 4,668,246 relates to polyamino alkenyl or alkylsuccinimides which have been modified by treatment with a lactone toyield polyamino alkenyl or alkyl succinimides wherein one or more of thebasic nitrogens of the polyamino moiety is substituted with ahydrocarbylcarbonylalkylene group. The additives are useful asdispersants in lubricating oils, gasolines, marine crank case oils andhydraulic oils.

Additional exemplary prior art disclosures which are expresslyincorporated herein by reference in their entirely are U.S. Pat. Nos.:2,890,208; 3,087,936; 3,131,150; 3,154,560; 3,172,892; 3,198,736;3,215,707; 3,231,587; 3,325,484; 3,269,946; 3,272,743; 3,272,746;3,278,550; 3,284,409; 3,284,417; 3,288,714; 3,361,673; 3,390,086;3,401,118; 3,403,102; 3,455,827; 3,562,159; 3,576,743; 3,632,510;3,684,771; 3,792,061; 3,799,877; 3,836,470; 3,836,471; 3,838,050;3,838,052; 3,879,308; 3,912,764; 3,927,041; 3,850,341; 4,110,349;4,116,875; 4,151,173; 4,195,976; 4,517,104; 4,536,547; and Re. 26,330.

SUMMARY OF THE INVENTION

It is a principal object of this invention to provide a novel class ofpoly (C₅ -C₉ lactone) adduct dispersants.

Another object is to provide a process for preparing a novel class ofdispersants from C₅ -C₉ lactones and Mannich base derivatives ofN-(hydroxyaryl) hydrocarbyl-substituted imides which containlactone-reactive amine functionality.

Another object is to provide a process for preparing novel classes ofpolymeric dispersants from C₅ -C₉ lactones, hydroxyaryl amines, longchain hydrocarbyl-substituted dicarboxylic acid producing materials di-or polyamines, and aldehydes.

Yet another object is to provide a process for preparing novel polymericdispersants from C₅ -C₉ lactones and the reaction product of ahydrocarbyl-substituted dicarboxylic acid material and a hydroxyarylamine which has been further reacted with an amine and an aldehyde.

Still another object is to prepare novel polymeric dispersants byreacting a C₅ -C₉ lactone with the reaction product of ahydrocarbyl-substituted dicarboxylic acid material and an N-hydroxyarylamine, followed by reaction with an amine and an aldehyde.

Yet another object is to prepare poly(C₅ -C₉ lactone) modified Mannichbase adduct dispersants by reacting a C₅ -C₉ lactone with the reactionproduct of a hydroxyaryl amine, an amine and an aldehyde, followed byreaction with a hydrocarbyl-substituted dicarboxylic acid material.

Another object is to provide a process for preparing novel poly(C₅ -C₉lactone) modified Mannich base adduct dispersants by reacting an aminewith a C₅ -C₉ lactone to form an intermediate which is further reacted,in sequence, with an aldehyde, a hydroxyaryl amine, and ahydrocarbyl-substituted dicarboxylic acid material.

Another object is to provide a process for preparing novel polymersdispersants by simultaneously reacting an amine, a C₅ -C₉ lactone and analdehyde to form an intermediate adduct, followed by the sequentialreaction of the intermediate adduct with a hydroxyaryl amine and ahydrocarbyl-substituted dicarboxylic acid material.

A further object is to prepare novel poly(C₅ -C₉ lactone) adductdispersants by simultaneously reacting an amine, a C₅ -C₉ lactone, ahydroxyaryl amine and an aldehyde to form an intermediate product,followed by reaction of the intermediate product with ahydrocarbyl-substituted dicarboxylic acid material.

A further object is to provide lubricant compositions and concentratescontaining the novel poly (C₅ -C₉ lactone) modified Mannich base adductsof this invention.

Yet another object is to provide a novel class of oil solublepolylactone modified Mannich base dispersants from polyalkylenesubstituted acylating agents which have at least one lactone-reactiveamino group in their structure.

Still another object is to provide poly (C₅ -C₉ lactone) adducts fromMannich base derivatives of polyalkylene substituted N-hydroxyarylsuccinimides which contain at least one lactone-reactive amino group, aswell as lubricant compositions and concentrates containing such adducts.

Still another object is to provide metal complexes and otherpost-treated derivatives, e.g., borated derivatives, of the novelpoly(C₅ -C₉ lactone) modified Mannich base adducts of this invention, aswell as lubricant compositions and concentrates containing suchpost-treated derivatives.

The manner in which these and other objects can be achieved will beapparent from the detailed description of the invention which appearshereinbelow.

In one aspect of this invention, one or more of the above objects can beachieved by initiating the polymerization of a C.sub. 5-C₉ lactone bymeans of an amino function contained in a Mannich base derivative of apolyolefin substituted N-hydroxyaryl imide, wherein the polyolefin has anumber average molecular weight of about 300 to about 10,000, wherein apolyolefin substituted dicarboxylic acid acylating agent has beenneutralized with an amino phenol, and wherein the polyolefinsubstituted, neutralized acylating agent contains from about 0.70 toabout 2.0 dicarboxylic acid producing moieties, preferably acidanhydride moieties, per equivalent weight of polyolefin.

In another aspect, one or more of the objects of this invention can beachieved by heating a C₅ C₉ lactone such as E-caprolactone at atemperature of at least about 80° C., and preferably from about 90° C.,to about 180° C. with a Mannich base derivative of a N-hydroxyarylpolyalkylene succinimide initator wherein the polyalkylene ischaracterized by a number average molecular weight of about 300-10,000and wherein the initiator is characterized by the presence within itsstructure of from about 0.70 to about 2.0 succinic acid or succinic acidderivative moieties for each equivalent weight of polyalkylene; and, ina further aspect, one or more objects of this invention are achieved byproviding poly (C₅ -C₉ lactone) adducts produced by such a process.

One or more additional objects of this invention are achieved byreacting E-caprolactone with a polyalkylene succinic acylating agentwhich has been post-treated with a hydroxyaryl amine, a polyamine and analdehyde to introduce into the structure thereof at least onelactone-reactive amino group; one or more additional objects areaccomplished by providing poly (E-caprolactone) adducts produced by sucha process.

One or more objects of this invention can be illustrated in connectionwith the reaction between E-caprolactone and a Mannich base derivativeof a N-hydroxyaryl polyisobutenyl succinimide initiator having availableprimary amine functionality as follows: ##STR5## where n is a numberfrom 1 to 4, p is a number from 1 to 7, m has an average value of about0.2 to about 100, preferably from 1 to about 20, most preferably from 1to about 5, R' is hydrogen, an alkyl radical or a halogen radical, Rrepresents polyisobutylene having a number average molecular weight offrom about 700 to about 5,000, and the ratio (functionality) of succinicacid producing moieties is from about 0.70 to about 2.0 per equivalentweight of polyisobutylene. The above polymerization can be conductedwith or without a catalyst. However, it is generally preferred to employa catalyst such as stannous octanoate in an amount of from about 100 toabout 10,000 parts by weight of catalyst per one million parts ofE-caprolactone.

One or more additional objects can be illustrated in connection with thereaction between E-caprolactone and a Mannich base derivative of aN-hydroxyaryl polyalkylene succinimide initiator having secondary aminefunctionality, such as a polyisobutenyl bis-succinimide, as follows:##STR6## where n, and n', independently, are numbers from 1 to 4; p andp', independently, are numbers from 1 to 7; and m and z, independently,have a value of zero to about 10, preferably from 1 to about 20, mostpreferably from 1 to about 5, provided however that both m and z can notbe zero, R' represents H, a C₁ to C₃ alkyl radical or a halogen radical(e.g., Cl--, Br-- or I--), R represents polyisobutylne having a numberaverage molecular weight of from about 700 to about 5,000, and thefunctionality of succinic acid producing moieties is from about 0.7 toabout 2.0 per equivalent weight of polyisobutylene.

The novel poly (C₅ -C₉ lactone) modified Mannich base adducts of thisinvention are useful per se as an additive, e.g. a dispersant additive,for example in the same manner as disclosed in U.S. Pat. No. 3,219,666where prior art derivatives of polyalkenyl succinic acids and nitrogencompounds are used as dispersant/detergents in lubricants, especiallylubricants intended for use in the crankcase of internal combustionengines, gears, and power transmitting units. Accordingly, one or moreobjects of the invention are achieved by providing lubricating oilcompositions, e.g. automatic transmission fluids, heavy duty oilssuitable for use in the crankcases of gasoline and diesel engines, etc.containing the novel poly (C₅ -C₉ lactone) adducts of this invention.Such lubricating oil compositions may contain additional additives suchas viscosity index improvers, antioxidants, corrosion inhibitors,detergents, pour point depressants, antiwear agents, etc.

Still further objects are achieved by providing concentrate compositionscomprising from about 10 to about 80 wt. % of a normally liquid,substantially inert, organic solvent/diluent, e.g. mineral lubricatingoil, or other suitable solvent/diluent and from about 20 to about 90 wt.% of a poly (C₅ -C₉ lactone) adduct, as mentioned above and described inmore detail hereinafter.

DESCRIPTION OF THE PREFERRED EMBODIMENTS The Hydrocarbyl DicarboxylicAcid Material

The long chain hydrocarbyl substituted dicarboxylic acid material, i.e.acid or anhydride, or ester, used in the invention includes a long chainhydrocarbon, generally a polyolefin, substituted with 0.7 to 2.0,preferably 1.00 to 1.5, e.g. 1.05 to 1.3 moles, per mole of polyolefinof an alpha or beta unsaturated C₄ to C₁₀ dicarboxylic acid, oranhydride or ester thereof, such as fumaric acid, itaconic acid, maleicacid, maleic anhydride, chloromaleic acid, dimethyl fumarate,chloromaleic anhydride, etc.

Preferred olefin polymers for reaction with the unsaturated dicarboxylicacid material are polymers comprising a major molar amount of C₂ to C₁₀,e.g. C₂ to C₅ monoolefin. Such olefins include ethylene, propylene,butylene, pentene, octene-1, styrene, etc. The polymers can behomopolymers such as polyisobutylene, as well as copolymers of two ormore of such olefins such as copolymers of: ethylene and propylene;butylene and isobutylene; propylene and isobutylene; etc. Othercopolymers include those in which a minor molar amount of the copolymermonomers, e.g., a copolymer of isobutylene and butadiene; or a copolymerof ethylene, propylene and 1,4-hexadiene; etc.

In some cases, the olefin polymer may be completely saturated, forexample an ethylene-propylene copolymer made by a Ziegler-Nattasynthesis using hydrogen as a moderator to control molecular weight.

The olefin polymers will usually have a number average molecular weight(M_(n)) within the range of about 700 and about 10,000, more usuallybetween about 700 and about 5,000. Particularly useful olefin polymershave a number average molecular weight within the range of about 700 toabout 3000, and more preferably within the range of about 900 to about2,500 with approximately one terminal double bond per polymer chain. Anespecially useful starting material for a highly potent dispersantadditive made in accordance with this invention is polyisobutylene. Thenumber average molecular weight for such polymers can be determined byseveral known techniques. A convenient method for such determination isby gel permeation chromatography (GPC) which additionally providesmolecular weight distribution information, see W. W. Yau, J. J. Kirklandand D. D. Bly, "Modern Size Exclusion Liquid Chromatography", John Wileyand Sons, New York, 1979.

Processes for reacting the olefin polymer with the C₄ -C₁₀ unsaturateddicarboxylic acid material are known in the art. For example, the olefinpolymer and the dicarboxylic acid material simply may be heated togetheras disclosed in U.S. Pat. Nos. 3,361,673 and 3,401,118 to cause athermal "ene" reaction to take place; or, the olefin polymer can befirst halogenated, for example, chlorinated or brominated to about 1 to8, preferably 3 to 7 wt. % chlorine or bromine, based on the weight ofpolymer, by passing the chlorine or bromine through the polyolefin at atemperature of 100° to 250° C., e.g. 140° to 225° C. for about 0.5 to 10preferably 1 to 7 hours. The halogenated polymer may then be reactedwith sufficient unsaturated acid or anhydride at 100° to 250° C.,usually about 140° to 180° C. for about 0.5 to 10, e.g. 3 to 8 hours, sothe product obtained will contain about 1.0 to 1.5, preferably 1.06 to1.20, e.g. 1.10 moles of the unsaturated acid per mole of thehalogenated polymer. Processes of this general type are taught in U.S.Pat. Nos. 3,087,436; 3,172,892; 3,272,746 and others.

Alternatively, the olefin polymer, and the unsaturated acid material maybe mixed and heated while adding chlorine to the hot material. Processesof this type are disclosed in U.S. Pat. Nos. 3,215,707; 3,231,587;3,912,764; 4,110,349; 4,234,435; and in U.K. No. 1,440,219.

By the use of halogen, about 65 to 95 wt. % of the polyolefin, e.g.polyisobutylene normally will react with the dicarboxylic acid material.Upon carrying out a thermal reaction without the use of halogen or acatalyst, then usually only about 50 to 75 wt. % of the polyisobutylenewill react. Chlorination helps increase the reactivity. For convenience,the aforesaid functionality ratios of dicarboxylic acid producing unitsto polyolefin of 0.70 to 2.0, 1.00 to 1.5 and 1.05 to 1.3 are based uponthe total amount of polyolefin, that is the total of both the reactedand unreacted polyolefin, used to make the product.

The preferred long chain hydrocarbyl substituted dicarboxylic anhydridesto be used in this invention can be illustrated by the formula: ##STR7##wherein R is hydrocarbyl of from 50 to 300 carbon atoms, and preferablyis a polyolefin derived from a C₂ to C₁₀ (e.g., C₂ to C₅)mono-alpha-olefin.

THE HYDROXYARYL AMINE MATERIAL

The hydroxyaryl amines which are useful in this invention compriseN-hydroxyaryl amines of the formula

    H.sub.2 N--Ar--OH                                          III

where Ar represents ##STR8## and wherein r is 1 or 2. Illustrative ofsuch Ar groups are phenylene, ##STR9## biphenylene, ##STR10##naphthylene, ##STR11## and the like. The Ar group may be substitutedwith hydrocarbyl groups, e.g., alkyl groups containing 1 to 20 carbonatoms, or with 1 to 3 halogen radicals, e.g., chloro-, bromo-, or iodo-.

Preferred N-hydroxyaryl amine reactants are amino phenols of theformula: ##STR12## in which R' is hydrogen, an alkyl radical having from1 to 3 carbon atoms or a halogen radical such as the chloride or bromideradical.

Suitable aminophenols include 2-aminophenol, 3-aminophenol,4-aminophenol, 4-amino-3-methylphenol, 4-amino-3-chlorophenol,4-amino-2-bromophenol and 4-amino-3-ethylphenol.

Suitable amino-substituted polyhydroxyaryls are the aminocatechols, theamino resorcinols, and the aminohydroquinones, e.g.,4-amino-1,2-dihydroxybenzene, 3-amino-1,2-dihydroxybenzene,5-amino-1,3-dihydroxybenzene, 4-amino-1,3-dihydroxybenzene,2-amino-1,4-dihydroxybenzene, 3-amino-1,4-dihydroxybenzene and the like.

Suitable aminoaphthols include 1-amino-5-hydroxynaphthalene,1-amino-3-hydroxynaphthalene and the like.

THE AMINE MATERIAL

The amines which are useful in the present invention are those which canbe reacted simultaneously with an aldehyde, such as formaldehyde, in theMannich base reaction.

Useful amine compounds in the Mannich base reaction include polyaminesof about 2 to 60, e.g., 3 to 20, most preferably 3 to 10, total carbonatoms in the molecule. These amines may be hydrocarbyl amines or may behydrocarbyl amines including other non-interfering groups, e.g., alkoxygroups, amide groups, nitrile groups, imidazoline groups, and the like.Preferred amines are aliphatic saturated amines, including those of thegeneral formula: ##STR13## wherein R and R' are independently selectedfrom the group consisting of hydrogen; C₁ to C₂₅ straight or branchedchain alkyl radicals; C₁ l to C₁₂ l alkoxy C₂ to C₆ alkylene radicals;and C₁ to C₁₂ alkylamino C₂ to C₆ alkylene radicals; each s is the sameor a different number of from 2 to 6, preferably 2 to 4; and t is anumber of from 0 to 10, preferably 2 to 7. If t=0, then at least one ofR or R¹ ; must be H such that there are at least two of either primaryor secondary amino groups.

Non-limiting examples of suitable amine compounds include:1,2-diaminoethane; 1,3-diaminopropane; 1,4-diaminobutane;1,6-diaminohexane; polyethylene amines such as diethylene triamine;triethylene tetramine; tetraethylene pentamine; polypropylene aminessuch as 1,2-propylene diamine; di-(1,2-propylene) triamine;di-(1,3-propylene) triamine; N,N-dimethyl-1,3-diaminopropane;N,N-di-(2-aminoethyl) ethylene diamine; N-dodecyl-1,3-propane diamine;di-, and tri-tallow amines; amino morpholines such as N-(3-aminoproply)morpholine; etc.

Other useful amine compounds include: alicylic diamines such as1,4-di(aminomethyl) cyclohexane, and heterocyclic compounds such asmorpholines, imidazolines, and N-aminolakyl piperazines of the generalformula: ##STR14## wherein G is independently selected from the groupconsisting of hydrogen and omega-(non-tertiary)aminoalkylene radicals offrom 1 to 3 carbon atoms, and p is a number of from 1 to 4. Non-limitingexamples of such amines include 2-pentadecyl imidazoline;N-(2-aminoethyl) piperazine; etc.

Commercial mixtures of amine compounds advantageously may be used. Forexample, one process for preparing alkylene amines involves the reactionof an alkylene dihalide (such as ethylene dichloride or propylenedichloride) with ammonia, which results in a complex mixture of alkyleneamines wherein pairs of nitrogens are joined by alkylene groups, formingsuch compounds as diethylene triamine, triethylenetetramine,tetraethylene pentamine and isomeric piperazines. A low cost mixture ofpoly(ethyleneamines) compounds averaging about 5 to 7 nitrogen atoms permolecule are available commercially under trade names such as "PolyamineH", "Polyamine 400", "Dow Polyamine E-100", etc.

Useful amines also include polyoxalkylene polyamines such as those ofthe formulas:

    H.sub.2 N-alkylene-(-o-alkylene-)-.sub.m NH.sub.2          VII

where m has a value of about 3 to 70 and preferably 10 to 35; and

    R--alkylene-(-O-alkylene--.sub.n NH.sub.2 ]a               VIII

where n has a value of about 1 to 40 with the proviso that the sum ofall the n's is from about 3 to about 70 and preferably from about 6 toabout 35, R is a polyvalent saturated hydrocarbon radical of up to tencarbon atoms, and a is a number from 3 to 6. The alkylene groups iseither formula VII or VIII may be straight or branched chain containingabout 2 to 7, and preferably about 2 to 4 carbon atoms.

The above polyoxyalkylene polyamines, preferably polyoxyalkylenediamines and polyoxyalkylene triamines, may have average molecularweights ranging from about 200 to about 4,000 and preferably from about400 to about 2,000. The preferred polyoxyalkylene polyamines include thepolyoxyethylene and polyoxypropylene diamines and the polyoxypropylenetriamines having average molecular weight ranging from about 200 to2,000. The polyoxyalkylene polyamines are commercially available and maybe obtained, for example, from the Jefferson Chemical Company, Inc.under the trade name "Jeffamines D-230, D-400, D-1000, D-2000, T-403",etc.

THE ALDEHYDE MATERIAL

The aldehyde material which can be employed in this invention isrepresented by the formula:

    R"CHO                                                      IX

in which R" is a hydrogen or an aliphatic hydrocarbon radical havingfrom 1 to 4 carbon atoms. Examples of suitable aldehydes includeformaldehyde, paraformaldehyde, acetaldehyde and the like.

THE LACTONE MATERIAL

Useful lactone compounds for the process of this invention include thoselactones having at least five carbon atoms in the lactone ring, e.g. 5to 9 carbon atoms. Such lactones are capable of undergoing ring openingpolymerization by reaction with an amine group or a hydroxy group. Thelactones may be substituted or unsubstituted and the subtituents, ifany, may comprise, for example, C₁ to C₂₅ straight or branched chainalkyl; aryl, aralkyl, or cycloalkyl having 6 to 60 total carbon atoms;C₁ to C₁₂ alkoxy or other groups which would not interfere with the ringopening reaction and adduct formation. The preferred lactones have nomore than two substituent groups, and the more preferred lactones areunsubstituted.

Non-limiting examples of the useful lactone include delta-valerolactone,methyl-delta-valerolactone, E-caprolactone, methyl-E-caprolactone,dimethyl-E-caprolactone, methoxy-E-caprolactone,cyclohexyl-E-caprolactone, methylbenzyl-E-caprolactone, caprylolactone,methyl-caprylolactone, and the like, with E-caprolactone beingparticularly preferred.

The ring opening polymerization of the lactone by reaction with ahydroxy group or an amine group-containing material may be carried out,with or without a catalyst, simply by heating a mixture of the lactoneand the hydroxy group or amine group-containing material in a reactionvessel in the absence of a solvent at a temperature of from about 30° C.to about 200° C, more preferrably at a temperature of about 75° C. toabout 180° C., and most preferably about 90° to about 160° C., for asufficient period of time to effect polymerization. Optionally, asolvent for the monomer and/or polymer can be employed to controlviscosity and/or reaction rates.

PREPARATION OF THE LACTONE POLYMERS DISPERSANTS

In one preferred aspect of this invention, the novel poly(C₅ -C₉lactone) adducts are prepared by first reacting the long chainhydrocarbyl substituted dicarboxylic acid material with theN-hydroxyaryl amine material to form an intermediate N-(hydroxyaryl)hydrocarbyl dicarboxylic acid imide. In general, equimolar amounts ofthe hydrocarbyl substituted dicarboxylic acid material, such aspolyisobutylene succinic anhydride, and of the N-hydroxyaryl amine, suchas p-aminophenol, are dissolved in an inert solvent (i.e. a hydrocarbonsolvent such as toluene, xylene, or isooctane) and reacted at amoderately elevated temperature up to the reflux temperature of thesolvent used for sufficient time to complete the formation of theintermediate N-(hydroxyaryl)hydrocarbyl imide. Thereafter, the solventis removed under vacuum at an elevated temperature, generally, atapproximately 160° C. (1mm).

Alternatively, the intermediate is prepared by combining equimolaramounts of the hydrocarbyl substituted dicarboxylic acid material andthe N-(hydroxyaryl) amine and heating the resulting mixture at elevatedtemperature under a nitrogen purge in the absence of solvent. Theresulting N-(hydroxyaryl) hydrocarbyl substituted imides can beillustrated by the succinimides of the formula: ##STR15## where R and R'are as defined above.

In the second step of this preferred aspect of the invention, theN-(hydroxyaryl)hydrocarbyl imide intermediate is reacted with apolyfunctional diamine together with an aldehyde in the Mannich basereaction. In general, the reactants are admixed and reacted at anelevated temperature until the reaction is complete. This reaction maybe conducted in the presence of a solvent and in the presence of aquantity of mineral oil which is an effective solvent for theN-(hydroxyaryl)hydrocarbyl imide intermediate and for the finishedMannich base. This second step can be illustrated by the Mannich basereaction between the above N-(hydroxyphenyl) hydrocarbyl succinimideintermediate, or formula X, paraformaldehyde and ethylene diamine inaccordance with the following equation: ##STR16## wherein a is aninteger of 1 or 2, and R and R' are as defined above.

In the final step of the poly(C₅ -C₉ lactone adduct formation, inaccordance with this aspect of the invention, the intermediate formed bythe Mannich base reaction is reacted with a lactone polymer using atleast one residual amine functionality on the intermediate as the ringopening and polymerization initiator. This final step can be illustratedby the following equation wherein a C₅ -C₉ lactone, such asE-caprolactone, is opened and polymerized by means of the aminefunctionality on the Mannich base intermediate: ##STR17## where a=1,m-1-10 and R and R' are as defined above.

In another preferred aspect of the invention, the poly(C₅ -C₉ lactone)adducts are prepared by using the hydroxy functionality on theintermediate N-(hydroxyaryl) hydrocarbyl imide to open and polymerizethe C₅ -C₉ lactone and thereby form an intermediate, which intermediateis then admixed and reacted with the amine material and the aldehyde inthe Mannich base reaction. The overall reaction scheme of this aspect ofthe invention can be illustrated as follows: ##STR18## where m, a, R andR' are as previously defined.

In still other aspects of the invention, the order of reacting thevarious reactants is modified such that, for example, the N-hydroxyarylamine is first admixed and reacted with the amine material and aldehydein the Mannich base reaction. Thereafter, by the ring openingpolymerization of the C₅ -C₉ lactone is performed and the resulting poly(C₅ -C₉ lactone) intermediate adduct is reacted with the hydrocarbylsubstituted dicarboxylic acid material. The sequence of reactionsperformed in accordance with this aspect of the invention tends toresult in the formation of various dispersant isomers because of theplurality of functional groups which are available for initiating the C₅-C₉ ring opening and polymerization. However, for the sake ofillustration, this aspect of the invention may be represented by thefollowing equations. ##STR19## where m and R are as previously defined.

It is also contemplated to admix and react the amine material with theC₅ -C₉ lactone to form an intermediate poly(C₅ -C₉ lactone) adduct whichis then reacted in sequence with the aldehyde, the N-hydroxyaryl amineand the hydrocarbyl substituted dicarboxylic acid material. Similarly,in other aspects of the invention the amine material is admixed andreacted with the aldehyde and the C₅ -C₉ lactone to form a poly(C₅ -C₉lactone) intermediate which is then reacted in sequence with theN-hydroxyaryl amine and the hydrocarbyl substituted dicarboxylic acidmaterial. In still another alternative embodiment, the amine, C₅ -C₉lactone, N-hydroxyaryl amine and aldehyde are admixed and reacted,followed by reaction with the hydrocarbyl substituted dicarboxylic acidmaterial to form the poly(C₅ -C₉ lactone) adduct dispersant.

In one preferred embodiment of the invention, the C₅ -C₉ lactone isreacted with a polyisobutenyl succinimide which has been prepared byfirst reacting a polyisobutenyl succinic anhydride with an aminophenolto form an intermediate product, and then reacting the intermediateproduct with formaldehyde and a mixture of poly(ethyleneamines) in theMannich base reaction as outlined above. This reaction can be depictedgenerally as in be the following equation when the succinimide hasavailable primary amino functionality: ##STR20## where x is a numberfrom 1 to 4, y is a number from 1 to 10, preferably 3 to 7, m has anaverage value of from about 0.2 to about 100, preferably from 1 to about20, z is from 4 to 8, PIB represents polyisobutylene having a numberaverage molecular weight of from about 700 to about 10,000, preferablyabout 900 to about 3,000, and the ratio(functionality) of succinic acidmoieties is from about 0.7 to about 2.0 per equivalent weight ofpolyisobutylene, and more preferably from about 1.00 to about 1.5 perequivalent weight of polyisobutylene.

Catalysts useful in the promotion of the above-identified reaction areselected from the group consisting of stannous octanoate, stannoushexanoate, stannous oxalate, tetrabutyl titanate, a variety of metalorganic based catalysts, acid catalysts and amine catalysts, asdescribed on page 266, and forward in a book chapter authored by R. D.Lundberg and E. F. Cox entitled, "Kinetics and Mechanisms ofPolymerization: Ring Opening Polymerization"; edited by Frisch andReegen, published by Marcel Dekker in 1969, wherein stannous octanoateis an especially preferred catalysts. The catalyst may be added to thereaction mixture at any effective concentration level. However, thecatalyst generally is added at a concentration level of about 50 toabout 10,000 parts of catalyst per one million parts by weight of totalreaction mixture.

When initiating the polymerization of the lactone monomer under theconditions described herein, the lactone will react selectively firstwith primary amino groups present in the initiator molecule and form apolymer adduct containing the polylactone ester group and a terminalhydroxyl group. In the absence of a catalyst, any excess lactone monomerwill either react with a secondary amino group present in the initiatormolecule or with the hydroxyl group formed via the reaction of thelactone with the primary amino groups. In the presence of a catalyst,such as stannous octanoate, it is believed that the lactone preferablywill react somewhat more readily with the terminal hydroxyl group thanwith a secondary amino group thus producing a polylactone ester adduct.If the stoichiometry of the initiator is such that very few primaryamino groups are available, secondary amino groups will be converted topolylactone adducts. This preference towards reaction with the primaryamino groups results in an added benefit in those specific applicationswhere the presence of primary amines is considered to be deleterious toperformance (such as in diesel dispersancy). In those cases, the presentinvention provides a means for replacing the deleterious amine groupwith an amide function and a desirable hydroxyl group.

In the reactions shown above, the value of m or the average degree ofpolymerization (DP) of the lactone monomers may vary depending upon theintended application. At DP's of much greater than about 10, e.g.,greater than about 50, the polylactone adducts can exhibitcrystallinity; a characteristics which is undesirable in an oil solubledispersant due to the consequent high viscosity or even solid, oilproducts which can be obtained. However, at lower DP's, oil solubleadducts possessing low viscosity and desirable sludge and varnishinhibition characteristics are obtained. Accordingly, regardless of theidentity of the lactone, the average degree of polymerization (DP) ofthe lactone modified Mannich base dispersant additives of this inventionshould be between about 1 and about 100, more preferably between about 1and about 50, and most preferably between about 0.2 and about 20.

Further aspects of the present invention reside in the formation ofmetal complexes and other post-treatment derivatives, e.g., boratedderivatives, of the novel additives prepared in accordance with thisinvention. Suitable metal complexes may be formed in accordance withknown techniques of employing a reactive metal ion species during orafter the formation of the present C₅ -C₉ lactone derived dispersantmaterials. Complex-forming metal reactants include the nitrates,thiocyanates, halides, carboxylates, phosphates, thio-phosphates,sulfates, and borates of transition metals such as iron, cobalt, nickel,copper, chromium, manganese, molybdenum, tungsten, ruthenium, palladium,platinum, cadmium, lead, silver, mercury, antimony and the like. Priorart disclosures of these complexing reactions may be found in U.S. Pat.Nos. 3,306,908 and Re. 26,433.

Post-treatment compositions include those formed by reacting the noveladditives of the present invention with one or more post-treatingreagents, usually selected from the group consisting of boron oxide,boron oxide hydrate, boron halides, boron esters, boron acids, sulfur,sulfur chlorides, phosphorous sulfides and oxides, carboxylic acid oranhydride acylating agents, epoxides and episulfides and acrylonitriles.The reaction of such post-treating agents with the novel additives ofthis invention is carried out using procedures known in the art. Forexample, boration may be accomplished in accordance with the teachingsof U.S. Pat. No. 3,254,025 by treating the C₅ -C₉ lactone derivedadditive compound with a boron oxide, halide, ester or acid. Treatmentmay be carried out by adding about 1-3 wt. % of the boron compound,preferably boric acid, and heating and stirring the reaction mixture atabout 135° C. to 165° C. for 1 to 5 hours followed by nitrogen strippingand filtration, if desired. Mineral oil or inert organic solventsfacilitate the process.

THE COMPOSITIONS

The lactone modified, Mannich base adducts of the present invention havebeen found to possess very good dispersant properties as measured hereinin a wide variety of environments.

Accordingly, the lactone modified Mannich base adducts are used byincorporation and dissolution into an oleaginous material such as fuelsand lubricating oils.

When the dispersant adducts of this invention are used in normallyliquid petroleum fuels such as middle distillates boiling from about150° to 800° F., including kerosene, diesel fuels, home heating fueloil, jet fuels, etc., a concentration of the additive in the fuel in therange of typically from about 0.001 to about 0.5, and preferably 0.001to about 0.1 weight percent, based on the total weight of thecomposition, will usually be employed.

The lactone modified, Mannich base dispersants find their primaryutility in lubricating oil compositions which employ a base oil in whichthe additives are dissolved or dispersed.

Such base oils may be natural or synthetic although the natural baseoils will derive a greater benefit.

Thus, base oils suitable for use in preparing lubricating compositionsof present invention include those conventionally employed as crankcaselubricating oils for spark-ignited and compression-ignited internalcombustion engines, such as automobile and truck engines, marine andrailroad diesel engines, and the like. Advantageous results are alsoachieved by employing the dispersant additives of the present inventionin base oils conventionally employed in and/or adapted for use as powertransmitting fluids such as automatic transmission fluids, tractorfluids, universal tractor fluids and hydraulic fluids, heavy dutyhydraulic fluids, power steering fluids and the like. Gear lubricants,industrial oils, pump oils and other lubricating oil compositions canalso benefit from the incorporation therein of the additives of thepresent invention.

Thus, the additives of the present invention may be suitablyincorporated into synthetic base oils such as alkyl esters ofdicarboxylic acids, polyglycols and alcohols, polyalphaolefins, alkylbenzenes, organic esters of phosphoric acids, polysilicone oils, etc.

Natural base oils include mineral lubricating oils which may vary widelyas to their crude source, e.g., whether paraffinic, naphthenic, mixed,paraffinic-naphthenic, and the like; as well as to their formation,e.g., distillation range, straight run or cracked, hydrofined, solventextracted and the like.

More specifically, the natural lubricating oil base stocks which can beused in the compositions of this invention may be straight minerallubricating oil or distillates derived from paraffinic, naphthenic,asphaltic, or mixed base crudes, or, if desired, various blends oils maybe employed as well as residuals, particularly those from whichasphaltic constituents have been removed. The oils may be refined byconventional methods using acid, alkali, and/or clay or other agentssuch as aluminum chloride, or they may be extracted oils produced, forexample, by solvent extraction with solvents of the type of phenol,sulfur dioxide, furfural, dichlorodiethyl ether, nitrobenzene,crotonaldehyde, molecular sieves, etc.

The lubricating oil base stock conveniently has a viscosity of typicallyabout 2.5 to about 12, and preferably about 2.5 to about 9 cs. at 100°C.

Thus, the lactone modified, Mannich base additives of the presentinvention can be employed in a lubricating oil, typically in a majoramount, and the dispersant additive, typically in a minor amount, whichis effective to impart enhanced dispersancy, relative to the absence ofthe additive. Additional conventional additives selected to meet theparticular requirements of a selected type of lubricating oilcomposition can be included as desired.

The dispersants of this invention are oil-soluble, dissolvable in oilwith the aid of a suitable solvent, or are stably dispersible materials.Oil-soluble, dissolvable, or stably dispersible as that terminology isused herein does not necessarily indicate that the materials aresoluble, dissolvable, miscible, or capable of being suspended in oil inall proportions. It does mean, however, that the dispersant additives,for instance, are soluble or stably dispersible in oil to an extentsufficient to exert their intended effect in the environment in whichthe oil is employed. Moreover, the additional incorporation of otheradditives may also permit incorporation of higher levels of a particulardispersant, if desired.

Accordingly, while any effective amount of the dispersant additives canbe incorporated into the lubricating oil composition, it is contemplatedthat such effective amount be sufficient to provide said lube oilcomposition with an amount of the additive of typically from about 0.10to about 15 e.g., 0.1 to 10, and preferably from about 0.1 to about 7wt. %, based on the weight of said composition.

The dispersant additives of the present invention can be incorporatedinto the lubricating oil in any convenient way. Thus, they can be addeddirectly to the oil by dispersing, or dissolving the same in the oil atthe desired level of concentration typically with the aid of a suitablesolvent such as toluene, or tetrahydrofuran. Such blending can occur atroom temperature or elevated temperatures. Alternatively, the dispersantadditives may be blended with a suitable oil-soluble solvent and baseoil to form a concentrate, and then blending the concentration withlubricating oil base stock to obtain the final formulation. Concentrateswill typically contain from about 20 to about 60 wt. %, by weightdispersant additive, and typically from about 80 to about 20%,preferably from about 60 to about 20% by weight base oil, based on theconcentrate weight.

The lubricating oil base stock for the dispersant additives of thepresent invention typically is adapted to perform a selected function bythe incorporation of additives therein to form lubricating oilcompositions (i.e., formulations).

Representative additives typically present in such formulations includeviscosity modifiers, corrosion inhibitors oxidation inhibitors, frictionmodifiers, other dispersants, anti-foaming agents, anti-wear agents,pour point depressants and the like.

Viscosity modifiers impart high and low temperature operability to thelubricating oil and permit it to remain shear stable at elevatedtemperatures and also exhibit acceptable viscosity or fluidity at lowtemperatures.

Viscosity modifiers are generally high molecular weight hydrocarbonpolymers including polyesters. The viscosity modifiers may also bederivatized to include other properties or functions, such as theaddition of dispersancy properties.

These oil soluble viscosity modifying polymers will generally havenumber average molecular weights of from 10³ to 10⁶, preferably 10⁴ to10⁶, e.g., 20,000 to 250,000, as determined by gel permeationchromatography or membrane osmometry.

Representative examples of suitable viscosity modifiers are any of thetypes known to the art including polyisobutylene, copolymers of ethyleneand propylene, polymethacrylates, methacrylate copolymers, copolymers ofan unsaturated dicarboxylic acid and vinyl compound and interpolymers ofstyrene and acrylic esters.

Corrosion inhibitors, also known as anti-corrosive agents, reduce thedegradation of the metallic parts contacted by the lubricating oilcomposition. Illustrative of corrosion inhibitors are zincdialkyldithiophosphate, phosphosulfurized hydrocarbons and the productsobtained by reaction of a phosphosulfurized hydrocarbon with an alkalineearth metal oxide or hydroxide, preferably in the presence of analkylated phenol or of an alkylphenol thioester, and also preferably inthe presence of carbon dioxide. Phosphosulfurized hydrocarbons areprepared by reacting a suitable hydrocarbon such as a terpene, a heavypetroleum fraction of a C₂ to C₆ olefin polymer such as polyisobutylene,with from 5 to 30 wt. % of a sulfide of phosphorus for 1/2 to 15 hours,at a temperature in the range of 150° to 600° F. Neutralization of thephosphosulfurized hydrocarbon may be effected in the manner taught inU.S. Pat. No. 1,969,324.

Oxidation inhibitors reduce the tendency of minerals oils to deterioratein service which deterioration is evidenced by the products of oxidationsuch as sludge and varnish-like deposits on the metal surfaces. Suchoxidation inhibitors include alkaline earth metal salts ofalkylphenolthioesters having preferably C₅ to C₁₂ alkyl side chains,e.g., calcium nonylphenol sulfide, barium t-octylphenyl sulfide,dioctylphenylamine, phenylalphanaphthylamine, phosphosulfurized orsulfurized hydrocarbons, etc.

Friction modifiers serve to impart the proper friction characteristicsto lubricating oil compositions such as automatic transmission fluids.

Representative examples of suitable friction modifiers are found in U.S.Pat. No. 3,933,659 which discloses fatty acid esters and amides; U.S.Pat. No. 4,176,074 which describes molybdenum complexes ofpolyisobutyenyl succinic anhydride-amino alkanols; U.S. Pat. No.4,105,571 which discloses glycerol esters of dimerized fatty acids; U.S.Pat. No. 3,779,928 which discloses alkane phosphonic acid salts; U.S.Pat. No. 3,778,375 which discloses reaction products of a phosphonatewith an oleamide; U.S. Pat. No. 3,852,205 which disclosesS-carboxyalkylene hydro-carbyl succinimide, S-carboxyalkylenehydrocarbyl succinamic acid and mixtures thereof; U.S. Pat. No.3,879,306 which discloses N-(hydroxyalkyl)alkenyl-succinamic acids orsuccinimides: U.S. Pat. No. 3,932,290 which discloses reaction productsof di-(lower alkyl) phosphites and epoxides; and U.S. Pat. No. 4,028,258which discloses the alkylene oxide adduct of phosphosulfurizedN-(hydroxyalkyl) alkenyl succinimides. The disclosures of the abovereferences are herein incorporated by reference. The most preferredfriction modifiers are succinate esters, or metal salts thereof, ofhydrocarbyl substituted succinic acids or anhydrides and thiobisalkanols such as described in U.S. Pat. No. 4,344,853, disclosure ofthis patent also being herein incorporated by reference.

Dispersants maintain oil insolubles, resulting from oxidation duringuse, in suspension in the fluid thus preventing sludge flocculation andprecipitation or deposition on metal parts. Suitable dispersants includehigh molecular weight alkyl succinates, the reaction product ofoil-soluble polyisobutylene succinic anhydride with ethylene amines suchas tetraethylene pentamine and borated salts thereof.

Pour point depressants lower the temperature at which the fluid willflow or can be poured. Such depressants are well known. Typically ofthose additives which usefully optimize the low temperature fluidity ofthe fluid are C₈ -C₁₈ dialkylfumarate vinyl acetate copolymers,polymethacrylates, and wax naphthalene. Foam control can be provided byan antifoamant of the polysiloxane type, e.g., silicone oil andpolydimethyl siloxane.

Anti-wear agents, as their name implies, reduce wear of metal parts.Representatives of conventional anti-wear agents are zincdialkyldithiophosphate, zinc diaryldithiosphate and magnesium sulfonate.

Detergents and metal rust inhibitors include the metal salts ofsulphonic acids, alkyl phenols, sulfurized alkyl phenols, alkylsalicylates, naphthenates and other oil soluble mono-and dicarboxylicacids. Highly basic (viz, overbased) metal salts, such as highly basicalkaline earth metal sulfonates (especially Ca and Mg salts) arefrequently used as detergents. Representative examples of suchmaterials, and their methods of preparation, are found in co-pendingSer. No. 754,001, filed July 11, 1985, the disclosure of which is herebyincorporated by reference.

Some of these numerous additives can provide a multiplicity of effects,e.g., a dispersant-oxidation inhibitor. This approach is well known andneed not be further elaborated herein.

Compositions when containing these conventional additives are typicallyblended into the base oil in amounts which are effective to providetheir normal attendant function. Representative effective amounts ofsuch additives are illustrated as follows:

    ______________________________________                                                           Broad    Preferred                                                            Wt. %    Wt. %                                             Additive           a.i.     a.i.                                              ______________________________________                                        Viscosity Modifier  .01-12  .01-4                                             Corrosion Inhibitor                                                                              0.01-5   .01-1.5                                           Oxidation inhibitor                                                                              0.01-1   .01-1.5                                           Dispersant          0.1-20  0.1-8                                             Pour Point Depressant                                                                            0.01-5   .01-1.5                                           Anti-Foaming Agents                                                                              0.001-3  .001-0.15                                         Anti-Wear Agents   0.001-5  .001-1.5                                          Friction Modifiers 0.01-5   .01-1.5                                           Detergents/Rust Inhibitors                                                                        .01-20  .01-3                                             Mineral Oil Base   Balance  Balance                                           ______________________________________                                    

When other additives are employed, it may be desirable, although notnecessary, to prepare additive concentrates comprising concentratedsolutions or dispersions of the dispersant (in concentrates amountshereinabove described), together with one or more of said otheradditives (said concentrate when constituting an additive mixture beingreferred to herein as an additive-package) whereby several additives canbe added simultaneously to the base oil to form the lubricating oilcomposition. Dissolution of the additive concentrate into thelubricating oil may be facilitated by solvents and by mixing accompaniedwith mild heating, but this is not essential. The concentrate oradditive-package will typically be formulated to contain the dispersantadditive and optional additional additives in proper amounts to providethe desired concentration in the final formulation when theadditive-package is combined with a predetermined amount of baselubricant. Thus, the dispersant of the present invention can be added tosmall amounts of base oil or other compatible solvents along with otherdesirable additives to form additive-packages containing activeingredients in collective amounts of typically from about 2.5 to about90%, and preferably from about 5 to about 75%, and most preferably fromabout 8 to about 50% by weight additives in the appropriate proportionswith the remainder being base oil.

The final formulations may employ typically about 10 wt. % of theadditive-package with the remainder being base oil.

All of said weight percents expressed herein are based on activeingredient (A.I.) content of the additive, and/or upon the total weightof any additive-package, or formulation which will be the sum of theA.I. weight of each additive plus the weight of total oil or diluent.

This invention will be further understood by reference to the followingexamples, wherein all percentages and parts are percentages and parts byweight and all molecular weights are number average molecular weightsunless otherwise noted, and which include preferred embodiments of theinvention.

EXAMPLE C1 (COMPARATIVE EXAMPLE) Part A

A polyisobutenyl succinic anhydride (PIBSA) having an SA:PIB ratio of1.23 succinic anhydride (SA) moieties per polyisobutylene (PIB) moleculeof 1300 M_(n) was prepared by heating a mixture of 100 parts ofpolyisobutylene with 12.2 parts of maleic anhydride to a temperature ofabout 220° C. When the temperature reached 120° C., chlorine additionwas begun and 10.5 parts of chlorine at a constant rate were added tothe hot mixture for about 5 hours. The reaction mixture was then heatsoaked at 220° C. for about 1.5 hours and then stripped with nitrogenfor about 1 hour. The resulting polyisobutenyl succinic anhydride had anASTM Saponification Number (SAP) of 97 which calculates to a succinicanhydride (SA) to polyisobutylene (PIB) ratio of 1.23 based upon thestarting PIB as follows: ##EQU1##

The PIBSA product was 90 wt. % active ingredient (a.i.), the remainderbeing primarily unreacted PIB. the SA:PIB ratio of 1.23 is based uponthe total PIB charged to the reactor as starting material, i.e., boththe PIB which reacts and the PIB which remains unreacted. The PIBSA wasthen diluted with mineral oil solvent 150 neutral to produce a PIBSA ofSAP 97 and 59 wt. % active ingredient.

Part B

To 1626 g (1.0 mole) of PIBSA of Part A (diluted to 59% ai with S150Nsolvent neutral mineral oil having a viscosity of about 150 SSU at 100°C.) there was added 109g (1.0 mole) of 4-aminophenol and 336 g of SI50Nlubricating oil. The mixture was stirred in a reaction flask and heatedslowly to about 160° C. under a nitrogen blanket. The reaction mixturewas then soaked for about 3 hours at 150° C. with light nitrogenstripping. The filtered N-(hydroxyphenyl) succinimide product analyzedfor 0.68% nitrogen.

EXAMPLE C2 (Comparative Example)

A mixture containing 2310g (1.07 mole) of a polyisobutenyl succinicanhydride (SAP=52.2, ai=77.7 wt. %), 117.3g (1.07 mole) of 4-aminophenoland 1389g of S150N solvent neutral mineral oil was stirred and slowlyheated to 160° C. while under nitrogen blanket. The reaction mixture wasthen heated at 160° C. for 3 hours and filtered. The resulting oilsolution of N-(hydroxyphenyl) hydrocarbyl succinimide analyzed for 0.44wt. % nitrogen.

EXAMPLE C3 (Comparative Example)

About 200 g (0.097 mole) of the N-(hydroxyaryl) succinimide solutionprepared in accordance with EXAMPLE 1, Part B was mixed with 18.8 g(0.097 mole) of a commercial grade of poly(ethyleneamine) which was amixture of poly(ethyleneamines) averaging about 5 to 7 nitrogen permolecule, hereinafter referred to as PAM, 4.4g (0.15 mole) ofpara-formaldehyde (CH₂ O)_(x) and 24.97 g of S150N and reacted at 80° C.for one hour under nitrogen atmosphere. The reaction mixture was thenheated to 160° C. for one hour and stripped at 160° C. for another hour.The reaction product analyzed for 3.02 wt % nitrogen.

EXAMPLE 4

About 200g (0.097 mole) of the N-(hydroxylphenyl) hydrocarbylsuccinimide prepared in accordance with EXAMPLE 1, Part B, 18.8g (0.097mole) of PAM, 4.4g (0.15 mole) of CH₂ O and 27.18g of S150N were mixedin a reaction flask and heated to 80° C. for one hour. The reactionmixture was then heated to 160° C. for one hour and nitrogen strippedfor another hour. Then, 2.2g of E-caprolactone (CL) and 0.05 g ofstannous octanoate were added and the reaction mixture was heated at160° C. for 3 hours while under nitrogen blanket. The reaction productwas filtered and analyzed for 2.93 wt. % nitrogen.

EXAMPLE 5

The procedure of EXAMPLE 4 was repeated, except that 4.4 g of CL wereadded together with and 4.4 g of S150N. The reaction product analyzedfor 2.92 wt. % nitrogen.

EXAMPLE 6

The procedure of EXAMPLE 4 was repeated, except that 6.6 g of CL and 6.6g of S150N were added. The reaction product analyzed for 2.8 wt. %nitrogen.

EXAMPLE C7 (Comparative Example)

The procedure of EXAMPLE 3 was followed except that 200g (0.057 mole) ofthe succinimide of EXAMPLE 2 were mixed with 10.94g (0.056 mole) of PAM,2.55g of CH₂ O and 11.39 g of S150N. The oil solution analyzed for 1.91wt. % nitrogen.

EXAMPLE 8

The product prepared in EXAMPLE 7 was mixed with 2.23 g CL and 2.23 g ofS150N, and the mixture was heated at 160° C. for 3 hours. The filteredproduct analyzed for 1.87 wt. % nitrogen.

EXAMPLE 9

The procedure of EXAMPLE 8 was repeated, except that 4.47 g CL and 4.47g of S150N were used. The product analyzed for 1.80 wt. % nitrogen.

EXAMPLE 10

THe process of EXAMPLE 8 was repeated, except that 6.70 of CL and 670 gof S150N were used. The product analyzed for 1.78 wt. % nitrogen.

Table 1, which follows, summarizes the characteristics of the dispersantmaterials prepared in accordance with EXAMPLES C1-10.

                                      TABLE 1                                     __________________________________________________________________________    PROPERTIES OF DISPERSANT ADDUCTS                                              DISPERSANT                                                                    ADDUCT, EX. NO.                                                                          SA:PIB.sup.(1)                                                                     WT % N                                                                             PIB, --M.sub.n.sup.(2)                                                              SAP.sup.(3)                                                                       PIBSA/H.sub.2 NOOH.sup.(4)                                                              % CL.sup.(5)                                                                       PIBSA/CH.sub.2 O.sup.(6)        __________________________________________________________________________    C.sub.1    1.23 0.68 1300  97  1         0    0                               C.sub.2    1.10 0.44 2250  52.2                                                                              1         0    0                               C.sub.3    1.23 3.02 1300  97  1         0    .65                             .sup. 4    1.23 2.93 1300  97  1         1    .65                             .sup. 5    1.23 2.92 1300  97  1         2    .65                             .sup. 6    1.23 2.81 1300  97  1         3    .65                             C.sub.7    1.10 1.91 2250  52.2                                                                              1         0    .67                             .sup. 8    1.10 1.87 2250  52.2                                                                              1         1    .67                             .sup. 9    1.10 1.80 2250  52.2                                                                              1         2    .67                             10         1.10 178  2250  1.78                                                                              1         3    .67                             __________________________________________________________________________     .sup.(1) ratio of succinic anhydride moeities (SA) per polyisobutylene        (PIB) molecule.                                                               .sup.(2) number average molecular weight of the PIB molecules                 .sup.(3) ASTM Saponification Number AMI-769-81                                .sup.(4) ratio of polyisobutylene succinic anhdride (PIBSA) moieties to       4aminophenol (H.sub.2 NOOH) moieties.                                         .sup.(5) weight percent of Ecaprolactone (CL) moieties in dispersant          adduct.                                                                       .sup.(6) ratio of polyisobutenyl succinic anhydride (PIBSA) moieties to       formaldehyde (CH.sub.2 O) moieties                                       

Sludge Inhibition and Varnish Inhibition Bench Tests

Samples of the dispersant adducts prepared as set forth in EXAMPLESC1-10 and the resulting were subjected to a standard sludge inhibitionbench test (SIB) and a standard varnish inhibition bench test (VIB).Samples of commerical PIBSA-PAM dispersants were also subjected to theSIB and VIB tests to provide a basis of comparison between the adductsof this invention and the corresponding prior art PIBSA-PAM and Mannichbase derivative dispersants.

The SIB and VIB tests forecast the performance of a lubricant in agasoline engine. These tests are described below:

The SIB Test employs a used crankcase mineral lubricating oilcomposition having an original visocity of about 325 SSU at 37.8° C.that has been used in a taxicab driven generally for short trips onlythereby causing a build up of a high concentration of sludge precursors.The oil used contains only a refined base mineral oil, a viscosity indeximprover, a pour point depressant and a zinc dialkyldithiophosphateanti-wear additive. The oil contains no sludge dispersants. Such usedoil is acquired by draining and refilling taxicab crankcases at about1,000-2,000 mile intervals.

The SIB Test is conducted in the following manner: The used crankcaseoil is freed of sludge by centrifuging for one half hour at about 39,000gravities (gs). The resulting clear bright red oil is then decanted fromthe insoluble sludge particles. However, the supernatant oil stillcontains oil-soluble sludge precursors which, under the conditionsemployed by this test, will tend to form additional oil-insolubledeposits of sludge. The sludge inhibiting properties of the additivesbeing tested are determined by adding to portions of the used oil 0.5wt. %, on an active basis, of the particular additive being tested. Tengrams of each oil sample being tested is placed in a stainless steelcentrifuge tube and is heated at 140° C. for 16 hours in the presence ofair. Following the heating, the tube containing the oil being tested iscooled and then centrifuged for 30 minutes at about 39,000 gs. Anydeposits of new sludge that form in this step are separated from the oilby decanting supernatant oil and then carefully washed with 15 ml. ofpentane to remove all remaining oils from the sludge. The weight, inmilligrams, of the new solid sludge that forms in the test is determinedby drying the residue and weighing it. The results are reported asmilligrams of sludge per ten grams of oil, thus measuring differences assmall as one part per ten thousand. The less new sludge formed, the moreeffective is the additive as a dispersant. In other words, if theadditive is effective, it will hold at least a portion of the new sludgethat forms on heating and oxidation, stably suspended in the oil so thatit does not precipitate during the centrifuging period.

In the VIB Test, a test sample consisting of ten grams of lubricatingoil containing 0.5 wt. %, on an active basis, of the additive beingevaluated is used. The test oil is a commercial lubricating oil obtainedfrom a taxi after about 2000 miles of driving with said lubricating oil.Each sample is heat soaked overnight at about 140° C. and thereaftercentrifuged to remove the sludge. The supernatant fluid of each sampleis subjected to heat cycling from about 150° C. to room temperature overa period of 3.5 hours at a frequency of about two cycles per minute.During the heating phase, a gas containing a mixture of 0.7 volumepercent SO₂, 1.4 volume percent NO and the balance air is bubbledthrough the test samples and during the cooling phase, water vapor wasbubbled through the test samples. At the end of the test period, whichtesting cycle can be repeated as necessary to determine the inhibitingeffect of any additive, the wall surfaces of the test flasks in whichthe samples are contained are visually evaluated as to the varnishinhibition. The amount of varnish deposited on the walls is rated atvalues of from one to eleven with the higher number being the greateramount of varnish. It has been found that this test forecasts thevarnish results obtained as a consequence of carrying out the ASTM MS-VDengine test which is described more fully hereinbelow.

Table 2, which follows, summarizes the compositions tested and the testresults.

                                      TABLE 2                                     __________________________________________________________________________    SLUDGE INHIBITION AND VARNISH INHIBITION BENCH TESTS                          EXAMPLE                    PIB          MANNICH BASE                          NO        SAMPLE                                                                              SA:PIB                                                                             WT. % N                                                                             --M.sub.n                                                                        % CL                                                                              SIB.sup.1                                                                        VIB.sup.1                                                                        DERIVATIVE                            __________________________________________________________________________    1               1.23 0.68  1300                                                                             0   9.88                                                                             6  NO                                    2               1.10 0.44  2250                                                                             0   8.94                                                                             5  NO                                    3               1.23 3.02  1300                                                                             0   0.62                                                                             3  YES                                   4               1.23 2.93  1300                                                                             1   1.19                                                                             3  YES                                   5               1.23 2.92  1300                                                                             2   1.13                                                                             3  YES                                   6               1.23 2.81  1300                                                                             3   0.02                                                                              31/2                                                                            YES                                   7               1.10 1.91  2250                                                                             0   3.50                                                                             4  YES                                   8               1.10 1.87  2250                                                                             1   2.56                                                                             4  YES                                   9               1.10 1.80  2250                                                                             2   3.06                                                                             3  YES                                   10              1.10 1.78  2250                                                                             3   2.50                                                                             3  YES                                   PIBSA-PAM                     0   3.19                                                                             5  YES                                   (COMPARATIVE)                                                                 PIBSA-PAM                     0   4.00                                                                             7  YES                                   (COMPARATIVE)                                                                 __________________________________________________________________________     .sup.1 mg sludge per 10 mg of oil in note 1. (rated on basis of 1 to 10,      being the best rating).                                                       .sup. 2 varnish rating visual (rated 1 to 11, 1 being the best rating).  

The data in Table 2 shows that the VIB and SIB values of the variouspolycaprolactone modified Mannich base adducts are generally improvedover the controls with increasing caprolactone content. In all practicalsystems the values obtained using the polycaprolactone modified Mannichbase adducts of this invention are within acceptable limits.

EXAMPLE 11 Part A

The procedure of Example C1, Part A, was repeated, except that the PBIhad a number average molecular weight (M_(n)) of 2250. The resultingPIBSA had a SAP of 52.4 and an SA:PIB ratio of 1.10 and 78.9 wt. % a.i.

Part B

To 214.5 g. of the PIBSA of Part A, there was added 10.9 g of4-aminophenol and 134 g. of S150N mineral oil. The mixture was stirredin a reaction flask and heated slowly to about 160° C. under a nitrogenblanket. The reaction mixture was then heated for about 3 hours at 160°C. with nitrogen stripping.

Part C

To the PIBSA-aminophenol reaction mixture obtained in Part B, there wasadded 9.5 g of tetraethylene-pentamine (TEPA), and 3.6 g of CH₂ O. Theresulting mixture was heated at 80° C. for about 2 hours with nitrogenstripping to form a Mannich base dispersant.

Part D

To the Mannich base dispersant prepared in part C, there was added 4 gof CL and 0.1 g of stannous octanoate as a catalyst. The reactionmixture was heated for about 2 hours at 160° C. The resultingpolycaprolactone modified Mannich base dispersant was nitrogen strippedfor about 1/2 hour and filtered, and subjected to the standard SIB andVIB tests. The test results are shown in Table 3.

EXAMPLE 12

To 223 g of a PIBSA-aminophenol adduct, which was prepared in a mannersimilar to that described in EXAMPLE 11, Part B, there were added 4.0 gof CL, 0.1 g of SnOct₂ and 134 g of S150N mineral oil. The mixture wasthen heated at 160° C. for about 1 hour. To the resulting solution therewas added 9.5 g of TEPA and 3.6 g of CH₂ O.

                                      TABLE 3                                     __________________________________________________________________________                                                    VIS-                          EXAMPLE   PIBSA                                                                             H.sub.2 NφOH                                                                    TEPA                                                                              CH.sub.2 O                                                                        CL S150N                                                                             SnOct.sub.2.sup.1                                                                          COSITY                        NO.       g   g     g   g   g  g   g    HAZE.sup.2                                                                         % N                                                                              CST.sup.3 169                                                                 100° C.                                                                         SIB                                                                              VIB               __________________________________________________________________________    11        214.5                                                                             10.9  9.5 3.6 4  134 0.1  4.3  1.23                                                                             1306     0.99                                                                             4                 12        214.5                                                                             10.9  9.5 3.6 4  134 0.1  200  1.04                                                                              149     2.73                                                                             4                 13        214.5                                                                             10.9  9.5 3.6 4  134 0.1   88  1.09                                                                              591     2.15                                                                             4                 14        214.5                                                                             10.9  9.5 3.6 4  134 0.1   7   1.10                                                                             1219     1.82                                                                             4                 15        214.5                                                                             10.9  9.5 3.6 4  134 0.1   40  1.06                                                                             1199     1.32                                                                             4                 16        214.5                                                                             10.9  9.5 3.6 4  134 0.1  139  1.13                                                                              995     2.23                                                                             5                 17        214.5                                                                             10.9  9.5 3.6 4  134 0.1   74  1.07                                                                              857     1.90                                                                             4                 18  (Control)                                                                           214.5                                                                             10.9  9.5 3.6 -- 134 --   5.5  1.20                                                                             1049     5.26                                                                             3-4               __________________________________________________________________________     .sup.1 stannous octoanate catalyst                                            .sup.2 nephelometer reading                                                   .sup.3 centistokes                                                            .sup.4 tetraethylene pentamine                                           

The mixture was then heated at 80° C. for 1 hour, at 130° C. for 1 hour,and at 160° C. for 2 hours. The resulting solution was nitrogenstripped, filtered and subjected to the standard SIB and VIB tests. Theresults of these test are shown in Table 3.

EXAMPLE 13

A TEPA-polycaprolactone adduct was prepared by heating a mixture of 9.5g of TEPA, 4.0 g of CL, 0.1 g of SnOct₂ and 134 g of S150N mineral oilat 150° C. for 1 hour. The resulting soluton was cooled and mixed with3.6 g of CH₂ O and 223 g of a PIBSA-aminophenol prepared in accordancewith the procedure of EXAMPLE 11, Part B. The reaction mixture washeated at 80° C. for 1 hour, at 130° C. for 1 hour, and 160° C. for 2hours, and was then nitrogen stripped, filtered, and subjected to thestandard SIB and VIB tests. The results of these tests are summarized inTable 3.

EXAMPLE 14

10.9 g of 4-aminophenol, 9.5 g of TEPA, 3.6 g of CH₂ O and 134 g ofS150N mineral oil were added to a reaction flask and at 80° C. for 1hour. Thereafter, 4 g. of CL and 0.1 g of SnOct₂ were added to the flaskand heating was continued for 1 hour at 160° C. 214.5 g of PIBSA, whichwas prepared in a manner similar to that set forth in EXAMPLE 11, PartA, was added to the reaction flask and the admixture was heated at 160°C. for 2 hours. The resulting polycaprolactone modified Mannich basedispersant solution was then filtered and subjected to the standard SIBand VIB tests. The results of these tests are summarized in Table 3.

EXAMPLE 15

9.5 g of TEPA, 4.0 of CL, 0.1 g of SnOct₂ and 134 g of S150N mineral oilwere admixed and heated at 160° C. for 1 hour. The reaction mass wasthen cooled. 3.6 g of CH₂ O, 10.9 g of 4-aminophenol and 100 g oftoluene were then added to the reaction mass and the resulting admixturewas heated at 80° C. for 1 hour. 214.5 g of the PIBSA prepared inaccordance with EXAMPLE 11, Part A, were then added to the reactionmixture and the mixture was heated at 160° C. for 2 hours and filtered.The resulting polycapro-lactone modified Mannich base dispersant wassubjected to the standard SIB and VIB tests. The results of these testsare summarized in Table 3.

EXAMPLE 16

9.5 of TEPA, 4.0 g of CL, 0.1 g of SnOct₂ and 134 g of S150N mineral oilwere mixed in a reaction flask and heated at 80° C. for 1 hour. Next,10.9 g of 4-aminophenol and 100 g of toluene were added and theresulting mixture was heated for an additional hour at 80° C. Finally,214.5 g. of the PIBSA prepared in accordance with EXAMPLE 11, Part A,was added and the mixture was heated at 130° C. for 1 hour and then at160° C. for 2 hours to complete the formation of a polycaprolactonemodified Mannich base dispersant. The dispersant was subjected to thestandard SIB and VIB tests. The results of these tests are summarized inTable 3.

EXAMPLE 17

10.9 g of 4-aminophenol, 4.0 g of CL, 0.1 g of SnOct₂, 9.5 g of TEPA,3.6 g of CH₂ O and 134 g of S150N mineral oil were admixed and heated at80° C. for 1 hour. 214.5 g of the PIBSA prepared in accordance withEXAMPLE 11, Part A, was then added to the reaction mass and heating wascontinued for 2 hours at 160° C. The resulting dispersant solution wasthen filtered and subjected to the standard SIB and VIB tests. Theresults of these tests are summarized in Table 3.

EXAMPLE 18

The procedures of EXAMPLE 11 was repeated, except that the Mannich basedispersant was not reacted with CL. The characteristics of the Mannichbase dispersant (control) are also set forth in Table 3.

EXAMPLE 19

About 200 g of the product of Example 4 was mixed with about 4.1 g ofboric acid and heated to 163° C. while stirring and nitrogen sparging.The mixture was kept at 163° C. to 2 hours, sparged with nitrogen forone half hour, and filtered. The resulting product analyzed for 0.36 %boron.

EXAMPLE 20

About 200 g of the material prepared in accordance with Example 5 wasmixed with 2.75 g of boric acid. The mixture was heated to 163° C. andstirred over a period of two hours. The reaction mixture was heated at163° C. for another 2 hours while sparging with nitrogen. Filtered andcollected product analyzed for 0.90%N and 0.24% Boron.

As used in this specification and claims, the terms "dicarboxylic acidmaterial" and "dicarboxylic acid producing material" are usedsynonomously and are meant to describe dicarboxylic acids, anhydrides,ester, etc. Non-limiting examples of such materials include fumaricacid, itaconic acid, maleic acid, maleic anhydride, succinic acid,succinic anhydride, chloromaleic acid, dimethyl fumarate, chloromaleicanhydride, etc.

As will be evident to those skilled in the art, various modifications onthis invention can be made or followed, in light of the foregoingdisclosure and illustrative examples, tables and discussion, withoutdeparting from the spirit and scope of the disclosure or from the scopeof the invention as set forth in the following claims

What is claimed is:
 1. A poly(C₅ -C₉ lactone) modified Mannich basehydrocarbyl substituted C₄ -C₁₀ dicarboxylic acid producing materialuseful as an oil additive and formed by reacting a C₅ -C₉ lactone, anamine, an aldehyde, an N-hydroxyaryl amine and a hydrocarbyl substitutedC₄ -C₁₀ dicarboxylic acid producing material, said hydrocarbylsubstituted C₄ -C₁₀ dicarboxylic acid producing material being formed byreacting an olefin polymer of a C₂ -C₁₀ monoolefin having a numberaverage molecular weight of about 700 to about 10,000 and a C₄ -C₁₀monounsaturated dicarboxylic acid material, wherein there is an averageof 0.7 to about 2.0 dicarboxylic producing moieties per molecule of saidolefin polymer used in the reaction, and said poly (C₅ -C₉ lactone)modified Mannich base adduct containing the unit ##STR21## wherein m hasa average value of from 0.2 to about 100, and z is 4 to
 8. 2. The poly(C₅ -C₉ lactone) modified Mannich base adduct according to claim 1,wherein said adduct has been prepared by first reacting saidN-hydroxyaryl amine with said hydrocarbyl substituted dicarboxylic acidproducing material to form an N-hydroxyaryl hydrocarbyl substitutedimide, thereafter admixing said imide with said amine and said aldehydeand subjecting the admixture to a Mannich base reaction to form anintermediate adduct having a amino functional group capable ofinitiating lactone open ring polymerization, and then reacting saidlactone with said intermediate adduct.
 3. The poly (C₅ -C₉ lactone)modified Mannich base adduct according to claim 1, wherein said adducthas been prepared by first reacting said N-hydroxyaryl amine with saidhydrocarbyl substituted dicarboxylic acid producing material to form anN-hydroxyaryl hydrocarbyl substituted imide having a functional groupcapable of initiating lactone ring open polymerization, thereafterreacting said imide with said lactone to form an intermediate adduct,and then admixing said intermediate adduct with said amine and saidaldehyde and subjecting the admixture to a Mannich base reaction.
 4. Thepoly (C₅ -C₉ lactone) modified Mannich base adduct according to claim 1,wherein said adduct has been prepared by first reacting said amine andsaid lactone to form a poly (C₅ -C₉ lactone) intermediate adduct, andthereafter reacting with said adduct a mixture of said hydrocarbysubstituted dicarboxylic acid producing material, said aldehyde and saidN-hydroxyaryl amine.
 5. The poly (C₅ -C₉ lactone) modified Mannich baseadduct according to claim 1, wherein said adduct has been prepared byfirst reacting said amine with said N-hydroxyarylamine and said aldehydeto form a first Mannich base intermediate containing a functional groupcapable of ring opening polymerization of said lactone, thereafteradmixing and reacting said lactone with said first Mannich baseintermediate to form a second Mannich base intermediate, and thenadmixing and reacting said hydrocarbyl substituted dicarboxylic acidproducing material with said second Mannich base intermediate.
 6. Thepoly (C₅ -C₉ lactone) modified Mannich base adduct according to claim 1,wherein said adduct has been prepared by first reacting said amine withsaid lactone to form a first poly(C₅ -C₉ lactone) intermediate, followedby reacting said first intermediate with said aldehyde and saidN-hydroxyaryl hydroxyaryl amine to form a second intermediate, and thenby reacting said hydrocarbyl substituted dicarboxylic acid producingmaterial with said second Mannich base intermediate.
 7. The poly (C₅ -C₉lactone) modified Mannich base adduct according to claim 1, wherein saidadduct has been prepared by first reacting said amine with said aldehydeand said lactone to form a first poly(C₅ -C₉ lactone) intermediate,followed by reacting said N-hydroxyaryl amine with said firstintermediate to form a second intermediate, and then by reacting saidhydrocarbyl substituted dicarboxylic acid producing material with saidsecond intermediate.
 8. The poly (C₅ -C₉ lactone-modified Mannich baseadduct according to claim 1, wherein said adduct has been prepared byfirst reacting said amine with said lactone, said aldehyde and saidN-hydroxyaryl amine to form an intermediate poly(C₅ -C₉ lactone) adduct,followed by reacting said intermediate adduct with said hydrocarbylsubstituted dicarboxylic acid producing material.
 9. The poly (C₅ -C₉lactone) modified Mannicch base adduct according to claim 1, whereinsaid adduct has been prepared by first reacting said amine with saidlactone to form a first poly(C₅ -C₉ lactone) intermediate, and thenreacting said intermediate with said aldehyde and a second intermediateformed by reacting said N-hydroxyaryl amine with said hydrocarbylsubstituted dicarboxylic acid producing material.
 10. The poly (C₅ -C₉lactone) modified Mannich base adduct material according to claim 1,wherein said C₅ -C₉ lactone is E-caprolactone.
 11. The adduct materialaccording to claim 10, wherein said C₄ -C₁₀ dicarboxylic acid producingmaterial is maleic anhydride.
 12. The adduct material according to claim11, wherein said olefin polymer is polyisobutylene.
 13. The adductmaterial according to claim 12, wherein said amine is selected from thegroup consisting of polyamines of about 2 to 60 total carbon atoms andabout 2 to 12 nitrogen atoms in the molecule.
 14. The adduct materialaccording to claim 13, wherein said amine is an aliphatic saturatedamine having the formula ##STR22## wherein R and R' independently areselected from the group consisting of hydrogen, C₁ to C₂₅ straight orbranched chain alkyl radicals, C₁ to C₁₂ alkoxy C₂ to C₆ alkyleneradicals, and C₁ to C₁₂ alkylamino C₂ to C₆ alkylene radicals; each s isthe same or a different number of from 2 to 6; and t is a number of from0 to 10, with the provision that when t=0, at least one of R or R' mustbe H such that there are at least two of either primary or secondaryamino groups.
 15. The adduct material of claim 14, wherein said amine isselected from the group consisting of 1, 2-diaminoethane; 1,3-diaminopropane; 1, 4-diaminobutane; 1, 6-diaminohexane; diethylenetriamine; triethylene tetramine; tetraethylene pentamine; 1, 2-propylenediamine; di-(1, 2-propylene)triamine; di-(1, 3-propylene) triamine; N,N-dimethyl-1, 3-diaminopropane; N, N-di-(2-aminoethyl) ethylene diamine;and N-dodecyl-1, 3-propane diamine.
 16. The adduct material according toclaim 13, wherein said amine is selected from the group consisting ofalicyclic diamines, imidazolines, morpholines, and N-aminoalkylpiperazines of the general formula: ##STR23## wherein G is independentlyselected from the group consisting of hydrogen andomega-(non-tertiary)aminoalkylene radicals of from 1 to 3 carbon atoms,and p is a number of from 1 to
 4. 17. The adduct material according toclaim 13, wherein said amine is a mixture of poly(ethyleneamines)averaging about 5 to about 7 nitrogen atoms per molecule.
 18. The adductmaterial of claim 13, wherein said amine is a polyoxyalkylene polyaminehaving the formula:

    NH.sub.2 - alkylene -(0-alkylene)-.sub.m NH.sub.2

where m has a value of about 3 to 70; or

    R -[alkylene - (0-alkylene) -.sub.n NH.sub.2 ].sub.a

where n has a value of about 1 to 40 with the provision that the sum ofall the n's is from about 3 to about 70, R is a substituted saturatedhydrocarbon radical of up to ten carbon atoms, wherein the number ofsubstituents on the R group is represented by the value of "a", which isa number from 3 to
 6. 19. The adduct material according to claim 1,wherein the average value of m is 1 to about
 20. 20. The adduct materialaccording to claim 13, wherein the average value of m is 1 to about 20.21. The adduct material according to claim 14, wherein the average valueof m is 1 to about
 20. 22. The adduct according to claim 12, whereinthere are about 1.0 to 1.5 succinic anhydride units per polyisobutylenemoiety used in said reaction.
 23. The adduct according to claim 21,wherein there are about 1.0 to 1.5 succinic anhydride units perpolyisobutylene moiety used in said reaction.
 24. The adduct accordingto claim 13, wherein there are about 1.0 to 1.5 succinic anhydride unitsper polyisobutylene moiety used in said reaction.
 25. An oleaginouscomposition comprising a lubricating oil and a poly (C₅ -C₉ lactone)modified Mannich base adduct material prepared by reacting an amine, ahydrocarbyl substituted C₄ -C₁₀ dicarboxylic acid producing material, analdehyde, an N-hydroxy-arylamine and a C₅ -C₉ lactone, said hydrocarbylsubstituted C₄ -C₁₀ dicarboxylic acid producing material being formed byreacting an olefin polymer of a C₂ -C₁₀ monoolefin of 700 to about10,000 M_(n) with a C₄ -C₁₀ monounsaturated dicarboxylic acid material,wherein there is an average of from about 0.7 to about 2.0 dicarboxylicacid producing moieties per molecule of said olefin polymer used in thereaction, and wherein said poly (C₅ -C₉ lactone) modified Mannich baseadduct material contains the unit ##STR24## where m is a number havingan average value of from 0.2 to about 100, and z is 4 to
 8. 26. Anoleaginous composition according to claim 25, wherein said poly(C₅ -C₉lactone) modified Mannich base adduct material has been prepared byfirst reacting said N-hydroxyaryl amine with said hydrocarbylsubstituted dicarboxylic acid producing material to form anN-hydroxyaryl hydrocarbyl substituted imide thereafter admixing saidimide with said amine and said aldehyde and subjecting the admixture toa Mannich base reaction to form an intermediate adduct having an aminofunction group capable of initiating lactone open ring polymerization,and then reacting said lactone with said intermediate adduct.
 27. Anoleaginous composition according to claim 25, wherein said poly(C₅ -C₉lactone) modified Mannich base adduct material has been prepared byfirst reacting said N-hydroxyaryl amine with said hydrocarbylsubstituted dicarboxylic acid producing material to form anN-hydroxyaryl hydrocarbyl subsituted imide having a functional groupcapable of initiating lactone ring open polymerization, thereafterreacting said imide with said lactone to form an intermediate adduct,and then admixing said intermediate adduct with said amine and saidaldehyde and subjecting the admixture to a Mannich base reaction.
 28. Anoleaginous composition according to claim 25, wherein said poly(C₅ -C₉lactone) modified Mannich base adduct material has been prepared byfirst reacting said amine and said lactone to form a poly (C₅ -C₉lactone) intermediate adduct, and thereafter reacting with said adduct amixture of said hydrocarbyl substituted dicarboxylic acid producingmaterial, said aldehyde and said N-hydroxyaryl amine.
 29. An oleaginouscomposition according to claim 25, wherein said poly(C₅ -C₉ lactone)modified Mannich base adduct material has been prepared by firstreacting said amine with said N-hydroxyarylamine and said aldehyde toform a first Mannich base intermediate containing a functional groupcapable of ring opening polymerization of said lactone, thereafteradmixing and reacting said lactone with said first Mannich baseintermediate to form a second Mannich base intermediate, and thenadmixing and reacting said hydrocarbyl substituted dicarboxylic acidproducing material with said second Mannich base intermediate.
 30. Anoleaginous composition according to claim 25, wherein said poly(C₅ -C₉lactone) modified Mannich base adduct material has been prepared byfirst reacting said amine with said lactone to form a first poly(C₅ -C₉lactone) intermediate, followed by reacting said first intermediate withsaid aldehyde and said N-hydroxyaryl amine to form a secondintermediate, and then by reacting said hydrocarbyl substituteddicarboxylic acid producing material with said second intermediate. 31.An oleaginous composition according to claim 25, wherein said poly(C₅-C₉ lactone) modified Mannich base adduct material has been prepared byfirst reacting said amine with said aldehyde and said lactone to form afirst poly(C₅ -C₉ lactone) intermediate, followed by reacting saidN-hydroxyaryl amine with said first intermediate to form a secondintermediate, and then by reacting said hydrocarbyl substituteddicarboxylic acid producing material with said second intermediate. 32.An oleaginous composition according to claim 25, wherein said poly (C₅-C₉ lactone) modified Mannich base adduct material has been prepared byfirst reacting amine with said lactone, said aldehyde and saidN-hydroxyaryl amine to form an intermediate poly(C₅ -C₉ lactone) adduct,followed by reacting said intermediate adduct with said hydrocarbylsubstituted dicarboxylic acid producing material.
 33. An olegenouscomposition according to claim 25, wherein said poly(C₅ -C₉ lactone)modified Mannich base adduct material has been prepared by firstreacting said amine with said lactone to form a first poly(C₅ -C₉lactone) intermediate, and then reacting said intermediate with saidaldehyde and a second intermediate formed by reacting said N-hydroxyarylamine with said hydrocarbyl substituted dicarboxylic acid producingmaterial.
 34. The oleaginous composition according to claim 25, whereinsaid C₅ -C₉ lactone monomer is Ecaprolactone.
 35. A lubricating oilcomposition comprising lubricating oil and about 0.01 to 15 wt. % of thepoly (C₅ -C₉) lactone modified Mannich base adduct material of claim 1.36. A lubricating oil comprising a major amount of lubricating oil andabout 0.1 to 10 wt. % of the poly (C₅ -C₉) lactone modified Mannich baseadduct material of claim
 1. 37. A lubricating oil comprising a majoramount of lubricating oil and about 0.1 to 10 wt. % of the poly (C₅ -C₉)lactone modified Mannich base adduct material according to claim
 10. 38.A lubricating oil comprising a major amount of lubricating oil and about0.1 to 10 wt. % of the poly (C₅ -C₉) lactone modified Mannich baseadduct material according to claim
 12. 39. A lubricating oil comprisinga major amount of lubricating oil and about 0.1 to 10 wt. % of the poly(C₅ -C₉) lactone modified Mannich base adduct material according toclaim
 22. 40. A lubricating oil comprising a major amount of lubricatingoil and about 0.1 to 10 wt. % of the poly (C₅ C₉) lactone modifiedMannich base adduct material according to claim
 17. 41. A lubricatingoil composition containing 0.01 to 15 wt. %, based on the weight of thetotal composition, of a poly (C₅ -C₉ lactone) modified Mannich baseadduct material according to claim
 10. 42. A lubricating oil compositioncontaining 0.01 to 15 wt. %, based on the weight of the totalcomposition, of a poly (C₅ -C₉ lactone) modified Mannich base adductmaterial according to claim
 12. 43. A lubricating oil compositioncontaining 0.01 to 15 wt. %, based on the weight of the totalcomposition, of a poly (C₅ -C₉ lactone) modified Mannich base adductmaterial according to claim
 24. 44. A lubricating oil compositioncontaining 0.01 to 15 wt. %, based on the weight of the totalcomposition, of a poly (C₅ -C₉ lactone) modified Mannich base adductmaterial according to claim
 17. 45. An oil soluble dispersant useful asan oil additive, comprising the product of a reaction of:(I) ahydrocarbyl substitued C₄ to C₁₀ monounsaturated dicarboxylic acidproducing material formed by reacting olefin polymer of C₂ to C₁₀monoolefin having a molecular weight of about 700 to 5,000 and a C₄ toC₁₀ monounsaturated acid material, wherein there are 0.7 to 2.0dicarboxylic acid producing moieties per molecule of said olefin polymerin the reaction mixture; (II) a C₅ -C₉ lactone, wherein there are, onthe average, 0.2 to about 100 C₅ -C₉ lactone derived moieties per moietyof said hydrocarbyl substituted dicarboxylic acid material used in thereaction; (III) an aldehyde having the formula

    R"CHO,

where R is hydrogen or an aliphatic hydrocarbon radical having from 1 to4 carbon atoms; (IV) an amine; and (V) an N-hydroxyarylamine having theformula

    H.sub.2 N--Ar--OH,

where Ar represents ##STR25## where the Ar group may be substituted withhydrocarbyl groups or with 1 to 3 halogen radicals, and r is an integerof 1 or
 2. 46. An oil soluble dispersant according to claim 45, whereinsaid dispersant has been prepared by first reacting said N-hydroxyarylamine with said hydrocarbyl substituted dicarboxylic acid producingmaterial to form an N-hydroxyaryl hydrocarbyl substituted imide,thereafter admixing said imide with said amine and said aldehyde andsubjecting the admixture to a Mannich base reaction to form anintermediate adduct having an amino functional group capable ofinitiating lactone open ring polymerization, and then reacting saidlactone with said intermediate adduct.
 47. An oil soluble dispersantaccording to claim 43, wherein said dispersant has been prepared byfirst reacting said N-hydroxyaryl amine with said hydrocarbylsubstituted dicarboxylic acid producing material to form anN-hydroxyaryl hydrocarbyl subsituted imide having a functional groupcapable of initiating lactone ring open polymerization, thereafterreacting said imide with said lactone to form an intermediate adduct,and then admixing said intermediate adduct with said amine and saidaldehyde and subjecting the admixture to a Mannich base reaction.
 48. Anoil soluble dispersant according to claim 43, wherein said dispersanthas been prepared by first reacting said amine and said lactone to forma poly (C₅ -C₉ lactone) intermediate adduct, and thereafter reactingwith said adduct a mixture of said hydrocarbyl substituted dicarboxylicacid producing material, said aldehyde and said N-hydroxyaryl amine. 49.An oil soluble dispersant according to claim 43, wherein said dispersanthas been prepared by first reacting said amine with saidN-hydroxyarylamine and said aldehyde to form a first Mannich baseintermediate containing a functional group capable of ring openingpolymerization of said lactone, thereafter admixing and reacting saidlactone with said first Mannich base intermediate to form a secondMannich base intermediate, and then admixing and reacting saidhydrocarbyl substituted dicarboxylic acid producing material with saidsecond Mannich base intermediate.
 50. An oil soluble dispersantaccording to claim 43, wherein said dispersant has been prepared byfirst reacting said amine with said lactone to form a first poly(C₅ -C₉lactone) intermediate, followed by reacting said first intermediate withsaid aldehyde and said N-hydroxyaryl amine to form a secondintermediate, and then by reacting said hydrocarbyl substituteddicarboxylic acid producing material with said second intermediate. 51.An oil soluble dispersant according to claim 43, wherein said dispersanthas been prepared by first reacting said amine with said aldehyde andsaid lactone to form a first poly(C₅ -C₉ lactone) intermediate, followedby reacting said N-hydroxyaryl amine with said first intermediate toform a second intermediate, and then by reacting said hydrocarbylsubstituted dicarboxylic acid producing material with said secondintermediate.
 52. An oil soluble dispersant according to claim 43,wherein said dispersant has been prepared by reacting said amine withsaid lactone, said aldehyde and said N-hydroxyaryl amine to form anintermediate poly(C₅ -C₉ lactone) adduct, followed by reacting saidintermediate with said hydrocarbyl substituted dicarboxylic acidproducing material.
 53. An oil soluble dispersant according to claim 43,wherein said dispersant has been prepared by first reacting said aminewith said lactone to form a first poly(C₅ -C₉ lactone) intermediate, andthen reacting said intermediate with said aldehyde and a secondintermediate formed by reacting said Nhydroxyaryl amine with saidhydrocarbyl substituted dicarboxylic acid producing material.
 54. An oilsoluble dispersant according to claim 45, wherein said C₅ -C₉ lactone isE-caprolactone, and wherein said dispersant contains the unit ##STR26##wherein m is from 1 to about
 100. 55. An oil soluble dispersantaccording to claim 54, wherein said polyamine is selected from the groupconsisting of polyamines of about 2 to 60 total carbon atoms and about 2to 12 nitrogen atoms in the molecule.
 56. An oil soluble dispersantaccording to claim 55, wherein m is 1 to 20, and wherein said polyamineis an aliphatic saturated amine having the general formula ##STR27##wherein R and R' independently are selected from the group consisting ofhydrogen, C₁ to C₂₅ straight or branched chain alkyl radicals, C₁ to C₁₂alkoxy C₂ to C₆ alkylene radicals, and C₁ to C₁₂ alkylamino C₂ to C₆alkylene radicals; each s is the same or a different number of from 2 to6; and t is a number of from 0 to 10, with the proviso that when t=0, atleast one of R or R' must be H such that there are at least two ofeither primary or secondary amino groups.
 57. An oil soluble dispersantaccording to claim 56, wherein said polyamine is selected from the groupconsisting of 1,2-diaminoethane; 1,3-diaminopropane; 1,4-diaminobutane;1,6-diaminohexane; diethylene triamine; triethylene tetramine;tetraethylene pentamine; 1,2-propylene diamine;di(1,2-propylene)triamine; di-(1,3-propylene triamine;N,N-dimethyl-1,3-diaminopropane; N,N-di-(2-aminoethyl) ethylene diamine;and N-dodecyl-1,3-propane diamine.
 58. The oil soluble dispersant ofclaim 55, wherein said amine is selected from the group consistingalicyclic diamines, imidazoles, morpholines, and N-aminoalkylpiperazines of the general formula: R1 ? ##STR28## wherein G isindependently selected from the group consisting of hydrogen andomega-(non-tertiary)aminoalkylene radicals of from 1 to 3 carbon atoms,and p is a number of from 1 to
 4. 59. The oil soluble dispersantaccording to claim 55, wherein said polyamine is a mixture ofpoly(ethyleneamines) averaging about 5 to about 7 nitrogen atoms permolecule.
 60. The oil soluble dispersant according to claim 55, whereinsaid polyamine is a polyoxyalkylene polymine having the formula:

    NH.sub.2 - alkylene - (O-alkylene).sub.m - NH.sub.2

where m has a value of about 3 to 70: or

    R -[alkylene 0 (O-alkylene).sub.n - NH.sub.2 ].sub.a

where n has a value of about 1 to 40 with the provison that the sum ofall the n's is from about 3 to about 70, R is a substituted saturatedhydrocarbon radical of up to ten carbon atoms, wherein the number ofsubstituents on the R group is represented by the value of "a", which isa number from 3 to
 6. 61. An oil soluble reacton product useful as anoil additive comprising:(a) polymer consisting essentially of C₂ to C₁₀monoolefin, said polymer being of 700 to 10,000 molecular weight andsubstituted with succinic moieties selected from the group consisting ofacid, anhydride and ester groups, wherein there are about 0.7 to 2.0molar proportions of succinic moieties per molar proportion of saidpolymer, (b) amine containing 2 to 60 carbon atoms and 2 to 12 nitrogengroups, and (c) C₆ -C₉ lactone, (d) N-hydroxyaryl amine having theformula

    H.sub.2 N-Ar-OH,

where Ar represents ##STR29## wherein the Ar group may be substitutedwith hydrocarbyl groups or with 1 to 3 halogen groups, and r is aninterger of 1 or 2, and (e) aldehydes having the formula

    RCHO,

where R is hydrogen or an aliphatic hydrcarbon radical having 1 to 4carbon atoms; wherein there are, on the average, about 0.2 to 100 molarproportion of (e) per molar proportion of said oil soluble reactionproduct.
 62. The oil soluble reaction product of claim 61 wherein (a) isfirst reacted with (d) to form a first intermediate, wherein a mixtureof (b) and (e) is then reacted with said first intermediate to form asecond intermediate, and wherein (c) is then reacted with said secondintermediate.
 63. The oil soluble reaction product of claim 61 wherein(a) is first reacted with (d) to form a first intermediate, wherein (e)is then reacted with said first intermediate to form a secondintermediate, and wherein a mixture of (b) and (e) are then reacted withsaid second intermediate.
 64. The oil soluble reaction product of claim61 wherein (b) is reacted with (c) to form a first intermediate, wherein(a) is reacted with (d) to form a second intermediate, and wherein saidfirst intermediate is then reacted with a mixture of said secondintermediate and (e).
 65. The oil soluble reaction product of claim 61wherein (d) is reacted with (b) and (e) to form a first intermediate,wherein (c) is reacted with said first intermediate to form a secondintermediate, and wherein (a) is reacted with said second intermediate.66. The oil soluble reaction product of claim 61 wherein (b) is firstreacted with (c) to form an intermediate, and wherein said intermediateis then reacted with a mixture of (a), (d) and (e).
 67. The oil solublereaction product of claim 61 wherein (b) is first reacted with (c) toform a first intermediate, wherein a mixture of (e) and (d) is reactedwith said first intermediate to form a second intermediate, and whereinsaid second intermediate is reacted with (a).
 68. The oil solublereaction product of claim 61 wherein a mixture of (c), (b) and (e) isreacted to form a first intermediate, wherein (d) is reacted with saidfirst intermediate to form a second intermediate, and wherein (a) isthen reacted with said second intermediate.
 69. The oil soluble reactionproduct of claim 61 wherein a mixture of (b), (c), (d) and (e) is firstreacted to form an intermediate which is then reacted with (a).
 70. Theoil soluble reaction product according to claim 61, wherein (b) is analiphatic saturated amine having the general formula ##STR30## wherein Rand R' independently are selected from the group consisting of hydrogen,C₁ to C₂₅ straight or branched chain alkyl radicals, C₁ to C₁₂ alkoxy C₂to C₆ alkylene radicals, and C₁ to C₁₂ alkylamino C₂ to C₆ alkyleneradicals; each s is the same or a different number of from 2 to 6, and tis a number of from 0 to 10, with the provison that when t=0, at leastone of R or R' must be H such that there are at least two of eitherprimary or secondary amino groups.
 71. The oil soluble reaction productaccording to claim 70, wherein (b) is amine is selected from the groupconsisting of 1,2-diaminoethane; 1,3-diaminopropane; 1,4-diaminobutane;1,6-diaminohexane; diethylene triamine; triethylene tetramine;tetraethylene pentamine; 1,2-propylene diamine;di-(1,2-propylene)triamine; di-(1,3-propylene triamine;N,N-dimethyl-1,3-diaminopropane; N,N-di-(2-aminoethyl) ethylene diamine;and N-dodecyl-1,3-propane diamine.
 72. The oil soluble reaction productaccording to claim 61, wherein (b) is a mixture of poly(ethyleneamines)averaging about 5 to about 7 nitrogen atoms per molecule.
 73. The oilsoluble reaction product according to claim 61, wherein (a) ispolyisobutylene of about 700 to 3,000 molecular weight substituted withsuccinic anhydride moieties.
 74. The oil soluble reaction productaccording to claim 70, wherein (c) is E-caprolactone and wherein thereare about 1 to 20 molar proportions of (c) per molar proportion of saidreaction product.
 75. The oil soluble reaction product according toclaim 74, wherein (a) is a polyisobutylene of about 900 to about 2,500molecular weight substituted with succinic anhydride moieties.
 76. Theoil soluble reaction product according to Claim 74, wherein (b) is analiphatic saturated amine having the general formula ##STR31## wherein Rand R' independently are selected from the group consisting of hydrogen,C₁ to C₂₅ straight or branched chain alkyl radicals, C₁ to C₁₂ alkoxy C₂to C₆ alkylene radicals, and C₁ to C₁₂ alkylamino C₂ to C₆ alkyleneradicals; each s is the same or a different number of from 2 to 6, and tis a number of from 0 to 10, with the provison that when t=0, at leastone of R or R' is H such that there are at least two of either primaryor secondary amino groups.
 77. The oil soluble reacton product accordingto claim 76, wherein (b) is amine is selected from the group consistingof 1,2-diaminoethane; 1,3-diaminopropane; 1,4-diaminobutane;1,6-diaminohexane; diethylene triamine; triethylene tetramine;tetraethylene pentamine; 1,2-propylene diamine;di-(1,2-propylene)triamine; di-(1,3-propylene triamine;N,N-dimethyl-1,3-diaminopropane; N,N-di-(2-aminoethyl) ethylene diamine;and N-dodecyl-1,3-propane diamine.
 78. The oil soluble reaction productaccording to claim 74, wherein (b) is a mixture of poly(ethyleneamines)averaging about 5 to about 7 nitrogen atoms per molecule.
 79. Anoleaginous composition comprising a lubricating oil and the oil solubleadditive of claim
 61. 80. The oleaginous composition of claim 79,wherein said lactone is E-caprolactone and wherein there are, on theaverage, from about 1 to 20 molar proportions of lactone per molarproportion of said oil soluble additive.
 81. The oleaginous compositionaccording to claim 79, wherein said amine is an aliphatic saturatedamine having the general formula ##STR32## wherein R and R'independently are selected from the group consisting of hydrogen, C₁ toC₂₅ straight or branched chain alkyl radicals, C₁ to C₁₂ alkoxy C₂ to C₆alkylene radicals, and C₁ to C₁₂ alkylamino C₂ to C₆ alkylene radicals;each s is the same or a different number of from 2 to 6, and t is anumber of from 0 to 10, with the provison that when t=0, at least one ofR and R' is H such that there are at least two primary or secondaryamino groups present in said polyamine.
 82. The oleaginous compositionaccording to claim 79, wherein said polyamine is a mixture ofpoly(ethyleneamines) averaging about 5 to about 7 nitrogen atoms permolecule.
 83. The lubricating oil composition according to claim 79,wherein (a) is polyisobutylene of about 700 to 3,000 molecular weightsubstituted with succinic anhydride moieties.
 84. A lubricatingcrankcase motor oil composition for automotive vehicles and truckscomprising a major amount of lubricating oil; from about 0.01 to 15 wt.% of the oil soluble reaction product of claim 61; and an effectiveamount of a viscosity modifier.
 85. The compositon according to claim84, wherein said composition also contains an effective amount of ananti-wear agent.
 86. A lubricating crankcase motor oil composition forautomotive vehicles and trucks comprising a major amount of lubricatingoil; from about 0.01 to 15 wt. % of the oil soluble reaction product ofclaim 62; and an effective amount of a viscosity modifier.
 87. Thecompositon according to claim 86, wherein said composition also containsan effective amount of an anti-wear agent.
 88. An additive concentratecomprising about 20 to 80 wt. % lubricating oil and 20 to about 80 wt. %of an oil soluble reaction product which is a poly (C₅ -C₉ lactone)modified Mannich base according to claim
 61. 89. The additiveconcentrate according to claim 88, wherein said oil soluble reactionproduct has been prepared by first reacting said N-hydroxyaryl amine (d)with said polymer (a) to form a first intermediate, then reacting saidfirst intermediate with a mixture of said amine (b) and said aldehyde(e) to form a second intermediate, and finally reacting said lactone (c)with said second intermediate.
 90. The concentrate according to claim88, which also contains an effective amount of a viscosity modifier. 91.The concentrate according to claim 90, which also contains an effectiveamount of an antiwear agent.
 92. The concentrate according to claim 89,wherein said lactone is E-caprolactone, and wherein said oil solublereaction product contains, on the average, from 1 to 20 caprolactonemoieties per molecule of said monoolefin polymer.
 93. An additiveconcentrate according to claim 92, which also contains an effectiveamount of a viscosity modifier.
 94. An additive concentrate according toclaim 93, which also contains an effective amount of a zincdihydrocarbyl dithiophosphate.